Multi-purpose polymers, methods and compositons

ABSTRACT

Disclosed are multi-purpose alkali-swellable and alkali soluble associative polymers, which are the polymerization product of a monomer mixture comprising: (a) at least one acidic vinyl monomer; (b) at least one nonionic vinyl monomer; (c) a first associative monomer having a first hydrophobic end group; (d) a monomer selected from the group consisting of a second associative monomer having a second hydrophobic end, a semihydrophobic monomer and a combination thereof; and, optionally, (e) one or more crosslinking monomers or chain transfer agents. When monomer (d) is an associative monomer, the first and second hydrophobic end groups of monomers (c) and (d) have significantly different hydrophobic and/or steric character from one another. The multi-purpose associative polymers surprisingly provide desirable Theological and aesthetic properties in aqueous media.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the priority of U.S. ProvisionalApplication for Patent Serial No. 60/349,399 filed on Jan. 18, 2002,which is incorporated herein by reference. The following related,commonly assigned, application was filed concurrently herewith: U.S.patent application Ser. No. ______, which claims priority from U.S.Provisional Application for Patent Serial No. 60/349,608 filed on Jan.18, 2002.

TECHNICAL FIELD OF THE INVENTION

[0002] This invention relates to the field of anionic polymers, and inparticular, to alkali-swellable and alkali-soluble associative polymers.

BACKGROUND OF THE INVENTION

[0003] An associative polymer contains pendant groups capable of formingnon-specific “associations” with other groups in the polymer or othermaterials in the medium in which the polymer is present. Generally thependant group has both hydrophobic and hydrophilic regions and theassociations are generally based on hydrophobic interactions. Hydrogenbonding associations between hydrophilic groups have also been seenunder some pH conditions. According to theory, such associations resultin thickening by the formation of interpolymer networks above a criticalpolymer overlap concentration.

[0004] Hydrophobically modified alkali-swellable or alkali solubleemulsion polymers, conventionally referred to as HASE polymers, areassociative polymers that are typically polymerized as stable emulsionsat low pH (pH <4.5) but become water swellable or soluble at nearneutral to neutral pH (pH >5.5-7). Typical HASE polymers are vinyladdition copolymers of pH sensitive or hydrophilic monomers, hydrophobicmonomers and an “associative monomer”. The associative monomer has apolymerizable end group, a hydrophilic midsection and a hydrophobic endgroup. An extensive review of HASE polymers is found in Gregory D. Shay,Chapter 25, “Alkali-Swellable and Alkali-Soluble Thickener Technology AReview”, Polymers in Aqueous Media—Performance Through Association,Advances in Chemistry Series 223, J. Edward Glass (ed.), ACS, pp.457-494, Division Polymeric Materials, Washington, D.C. (1989), therelevant disclosures of which are incorporated herein by reference.

[0005] Conventional HASE polymers generally contain a single associativemonomer. Conventional HASE polymers may be derived from associativemonomers having a hydrophobic end group which is substantially a singlehydrocarbon moiety or from associative monomers having hydrophobic endgroups which are predominantly mixtures of alkyl groups having molecularformulas differing by about 2 carbon atoms with minor amounts of alkylgroups differing by up to about 6 carbon atoms, for example, alkylgroups derived from some natural fatty materials.

[0006] Conventional HASE polymers have been used as rheology modifiers,emulsifiers, stabilizers, solubilizers and pigment grinding additives inindustrial applications. However, HASE polymers have found limitedutility as rheology modifiers in aqueous formulations, because thethickening ability of HASE polymers tends to be relatively low atpractical use levels of about 1% or less. Increasing the amount of HASEpolymer not only is economically undesirable, but highly viscous HASEpolymer solutions can be difficult to handle during manufacturingprocesses on a commercial scale. In addition, increased thickening oftenoccurs at the expense of the optical clarity of the final product, whichis undesirable in certain personal care applications especially for haircare. Consequently, the HASE polymers are conventionally combined withadditional rheology modifying polymers.

[0007] Some prior attempts have been made to enhance the thickeningability of associative polymers and improve their aqueous thickenerperformance. For example, U.S. Pat. No. 5,916,967 describes enhancingthe thickening ability of associative polymers by mixing the polymerwith two or more surfactants. Similarly, surfactant-thickenerinteractions are disclosed by C. E. Jones in “A Study of the Interactionof Hydrophobically-Modified Polyols with Surfactants”, Proceedings ofthe 4th World Surfactants Congress, CESIO, Barcelona, 2, 439-450 (1996)and by P. Reeve in “Tailoring the Properties of Polymeric RheologyModifiers to the Characteristics and Requirements of Personal CareFormulations”, Proceedings of International Federation of Society ofCosmetic Chemists, IFSCC, Budapest, 337-346 (April 1997).

[0008] An approach for improving the thickening properties of aqueoussolutions using macromonomer-derived associative polymers employingsurfactants as co-thickeners is disclosed in U.S. Pat. No. 5,292,843.European Patent Application No. 1,038,892A2 describes adding a mixtureof at least one multiphobe and at least one monophobe compound (as anadditive) particularly to improve the viscosity stability of an aqueoussystem containing at least one associative thickener. A method ofsuppressing the viscosity of HASE polymers in aqueous compositions bycomplexation of the hydrophobic moieties of the polymer withcyclodextrin compounds (capping agent additive) is disclosed in U.S.Pat. No. 5,137,571 and U.S. Pat. No. 6,063,857.

[0009] There is an ongoing, unresolved need and desire for anassociative polymer having improved Theological and aesthetic propertiesin an aqueous media. The multi-purpose alkali-swellable associativepolymers (ASAP) of the present invention surprisingly provide suchdesirable Theological and aesthetic properties in aqueous media.

SUMMARY OF THE INVENTION

[0010] The present invention discloses multi-purpose, alkali-swellableand alkali-soluble associative polymers, referred to herein as ASAP.

[0011] The ASAP of the present invention are the polymerization productof a monomer mixture comprising (a) at least one acidic vinyl monomer;(b) at least one nonionic vinyl monomer; (c) a first associative monomerhaving a first hydrophobic end group; (d) at least one monomer selectedfrom the group consisting of a second associative monomer having asecond hydrophobic end, a semihydrophobic monomer and a combinationthereof; and, optionally, (e) one or more crosslinking monomers or chaintransfer agents. When a second associative monomer (d) is included inthe polymerization, the first and second hydrophobic end groups of theassociative monomers (c) and (d) have significantly differenthydrophobic and/or steric character from one another.

[0012] The ASAP of the present invention can provide products havingTheological properties ranging from pourable liquids to non-pourablegels, as well as non-runny, yet flowable, compositions, withoutrequiring additional or auxiliary rheology modifiers. The inventivepolymers can also suspend abrasives, pigments, particulates, waterinsoluble materials, such as encapsulated oil beads, liposomes,capsules, gaseous bubbles, and the like.

[0013] Advantageously, the associative polymers of this invention can beemployed, without being limited thereto, in personal care products,health care products, household care products, non-household,institutional and industrial care products, and the like and inindustrial chemical processes and applications as, for example, rheologymodifiers, film formers, thickeners, emulsifiers, stabilizers,solubilizers, suspending agents, and pigment grinding additives. Thealkali-swellable, associative polymers are particularly useful asthickeners in textile treatment compositions for finishing, coating andprinting applications, and the like. The alkali-soluble, associativepolymers are particularly useful for thin viscosity, sprayable and foamcompositions.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] As used herein, the term ASAP includes the singular or pluralform and refers to acidic/anionic water-swellable or water-soluble,associative polymers, and salts-thereof, which contain two or morenon-identical hydrophobically modified polyoxyethylene groups, or whichcontain at least one hydrophobically modified polyoxyalkylene group andat least one non-hydrophobically modified polyoxyalkylene group. TheASAP may also optionally contain other monomer units, such ascrosslinking monomer units, or chain transfer agent units.

[0015] It has been surprisingly discovered that the ASAPs are suitablefor use in aqueous personal care, health care, household care, andinstitutional and industrial care (“I&I”) products and provide orattenuate rheology modification while retaining and enhancing thedesired performance and aesthetic properties of the polymer containingproducts.

[0016] The term “personal care products” as used herein includes,without being limited thereto, cosmetics, toiletries, cosmeceuticals,beauty aids, personal hygiene and cleansing products applied to thebody, including the skin, hair, scalp, and nails of humans and animals.The term “health care products” as used herein includes, without beinglimited thereto, pharmaceuticals, pharmacosmetics, oral care (mouth andteeth) products, such as oral suspensions, mouthwashes, toothpastes, andthe like, and over-the-counter products and appliances, such as patches,plasters and the like, externally applied to the body, including theskin, scalp, nails and mucous membranes of humans and animals, forameliorating a health-related or medical condition, for generallymaintaining hygiene or well-being, and the like. The term “householdcare products” as used herein includes, without being limited thereto,products employed in a domestic household for surface cleaning ormaintaining sanitary conditions, such as in the kitchen and bathroom,and laundry products for fabric care and cleaning, and the like. Theterm “institutional and industrial care” and “I&I” as used hereinincludes, without being limited thereto, products employed for surfacecleaning or maintaining sanitary conditions in institutional andindustrial environments, textile treatments, and the like.

[0017] As used herein and in the appended claims the term “theologicalproperties” and grammatical variations thereof, includes, withoutlimitation such properties as Brookfield viscosity, increase ordecrease-in viscosity in response to shear stress, flow characteristics,gel properties such as stiffness, resilience, flowability, and the like,foam properties such as foam stability, foam density, ability to hold apeak, and the like, and aerosol properties such as ability to formaerosol droplets when dispensed from propellant-based or mechanicalpump-type aerosol dispensers. The term “aesthetic property” andgrammatical variations thereof as applied to compositions refers tovisual and tactile psychosensory product properties, such as color,clarity, smoothness, tack, lubricity, texture, and the like.

[0018] The alkali-swellable, associative polymer embodiments of thisinvention are particularly useful as rheology modifiers in aqueoustextile treatment compositions. The term “textile” as used hereinincludes natural and synthetic fibers in woven or non-woven form,natural and synthetic leathers, and the like. Surprisingly, theinventive alkali-swellable ASAP have been found to be more efficientthickeners than conventional HASE polymer making them suitable for usein textile applications, such as printing, coating, saturation, dyeing,and like textile treatment operations.

[0019] The alkali-soluble, associative polymer embodiments of thisinvention are particularly useful as foam enhancers and as film formersin aqueous, and low VOC (volatile organic compounds) or high VOCpressurized or non-pressurized aerosols.

[0020] The term “aqueous” as applied to formulations or media means thatwater is present in an amount sufficient to at least swell or dissolvethe ASAP in the composition into which it is included.

[0021] The alkali-swellable and alkali-soluble associative polymers(ASAP) of the present invention are multi-purpose polymers, which arepreferably prepared by polymerizing a monomer mixture containing: (a) atleast one acidic vinyl monomer or salt thereof; (b) at least onenonionic vinyl monomer; (c) a first associative monomer having a firsthydrophobic end group; (d) at least one monomer selected from the groupconsisting of a second associative monomer having a second hydrophobicend group, a semihydrophobic monomer, and a combination thereof; and,optionally (e) one or more crosslinking monomer or chain transfer agent.When a second associative monomer (d) is included in the polymerizationmixture, the first and second hydrophobic end groups of the associativemonomers (c) and (d) are each independently selected from the same ordifferent hydrocarbon classes, with the proviso that when the first andsecond hydrophobic end groups are chosen from the same hydrocarbonclass, the molecular formulas of the two hydrophobic end groups differfrom one another by at least about 8 carbon atoms. When the polymercomprises two or more associative monomers, the weight ratio of at leasttwo of the associative monomers to one another in the mixture preferablyis in the range of about 1:1 to 100:1, more preferably 1:1 to about20:1, most preferably 1:1 to about 10:1.

[0022] In one preferred embodiment, the multi-purpose ASAP is thepolymerization product of a monomer mixture comprising, on a totalmonomer mixture weight basis:

[0023] (a) about 10 to about 75 weight percent of at least one acidicvinyl monomer or a salt thereof;

[0024] (b) about 10 to about 90 weight percent of at least one nonionicvinyl monomer;

[0025] (c) about 0.1 to about 25 weight percent of a first associativemonomer having a first hydrophobic end group;

[0026] (d) about 0.1 to about 25 weight percent of at least one monomerselected from the group consisting of a second associative monomerhaving a second hydrophobic end group, a semihydrophobic monomer and acombination thereof; and, optionally,

[0027] (e) about 0.01 to about 20 weight percent of one or more monomersselected from the group consisting of a crosslinking monomer, a chaintransfer agent, and a combination thereof.

[0028] A particularly preferred alkali-swellable associative polymerembodiment of the present invention is the product of polymerization ofa monomer mixture comprising, on a total monomer mixture weight basis:(a) about 30 to about 75 weight percent of at least one acidic vinylmonomer or a salt thereof; (b) at least about 25 weight percent, but notmore than 60 weight percent of at least one nonionic vinyl monomer; (c)about 0.5 to about 20 weight percent of a first associative monomerhaving a first hydrophobic end group; (d) about 0.5 to about 20 weightpercent of at least one monomer selected from the group consisting of asecond associative monomer having a second hydrophobic end group, asemihydrophobic monomer, and a combination thereof; and, optionally, (e)up to about 20 weight percent of a crosslinking monomer. When monomer(d) is a second associative monomer, the first and second hydrophobicend groups of associative monomers (c) and (d) are each independentlyselected from the same or different hydrocarbon classes. When the firstand second hydrophobic end groups are selected from the same hydrocarbonclass, the molecular formulas of the hydrophobic end groups differ by atleast about 8 carbon atoms. The associative polymers of this preferredembodiment are alkali-swellable and provide excellent rheology modifyingcharacteristics, providing relatively high viscosity to alkaline aqueoussystems in which the polymer is present. Examples of these preferredalkali-swellable polymers are provided in Tables 2A-2C, below.

[0029] Another preferred embodiment of the present invention is analkali-soluble, relatively low viscosity associative polymer. Thealkali-soluble associative polymer of this preferred embodiment is theproduct of polymerization of a monomer mixture comprising, on a totalmonomer mixture weight basis: (a) about 10 to about 30 weight percent ofat least one acidic vinyl monomer or a salt thereof; (b) more than 60weight percent of at least one nonionic vinyl monomer; (c) about 0.5 toabout 5 weight percent of at least one associative monomer having ahydrophobic end group; (d) about 0.5 to about 5 weight percent of atleast one semihydrophobic monomer having a polymerizable, unsaturatedend group and a polyoxyalkylene group covalently bonded thereto; and (e)about 0.5 to about 5 weight percent of a chain transfer agent. Thealkali-soluble associative polymers of this preferred embodiment providegood film-forming and humidity resistance properties, making themsuitable for compositions-, such as pumpable or sprayablehydro-alcoholic compositions, where a thin viscosity is desirable.Examples of these preferred alkali-soluble associative polymers areprovided in Table 2D, below.

[0030] Preferably, the hydrophobic end groups of the associativemonomers utilized in the polymers of the present invention are selectedfrom the group consisting of a C₁-C₄₀ linear alkyl, a C₈-C₄₀ branchedalkyl, a C₈-C₄₀ carbocyclic alkyl, an aryl-substituted C₂-C₄₀ alkyl, aC₂-C₄₀ alkyl-substituted phenyl, and a C₈-C₈₀ complex ester.

[0031] The first and second hydrophobic end groups of the associativemonomer components can be selected from the same or differenthydrocarbon classes. However, when a second associative monomer ispresent, and both the first and second associative monomers havehydrophobic end groups belonging to the same hydrocarbon class (e.g.,both hydrophobic end groups are C₈-C₄₀ linear alkyl groups) then, themolecular formulas of the hydrophobic end groups are selected to differfrom each other preferably by at least about 12 carbon atoms, morepreferably by at least about 10 carbon atoms, and most preferably by atleast about 8 carbon atoms.

[0032] In a particularly preferred embodiment, at least one associativemonomer has a hydrophobic end group which is a C₁₂-C₄₀ linear alkylgroup.

[0033] When more than two associative monomers are utilized to preparethe ASAP of the present invention, preferably at least two of theassociative monomers have hydrophobic end groups selected from differenthydrocarbon classes. When more than two associative monomers areutilized to prepare the ASAP of the present invention, and all of theutilized associative monomers have hydrophobic end groups selected fromthe same hydrocarbon class, the molecular formula of the hydrophobic endgroup having the largest number of carbon atoms preferably has at leastabout 12 more carbon atoms, more preferably at least about 10 morecarbon atoms, and most preferably at least about 8 more carbon atoms,than the molecular formula of the hydrophobic end group having the leastnumber of carbon atoms.

[0034] However, when the polymerization mixture comprises a combinationof a second associative monomer and a semihydrophobic monomer, there isno limitation as to the molecular formulas of the first and secondhydrophobic end groups of the associative monomers. When thepolymerization mixture includes a semihydrophobic monomer and two ormore associative monomers, the first and second associative monomers cancomprise any combination of first and second hydrophobic end groups,without limitation as to hydrocarbon class or number of carbon atoms inmolecular formulas of their respective hydrophobic end groups.

[0035] The terms “first” and “second “as used herein in relation toassociative monomers and their respective hydrophobic end groups meansthat two or more different associative monomers are employed, and arenot intended to imply any temporal relationship in the addition of themonomers to the reaction mixture, nor are the terms intended to connoteany functional difference between the monomers or hydrophobic endgroups. The term “(meth)acrylate” includes, alternatively, acrylate ormethacrylate, and the term “(meth)acrylamide” includes, alternatively,acrylamide or methacrylamide.

[0036] As used herein the term “alkyl” means a substituted orunsubstituted aliphatic hydrocarbon moiety; the term “carbocyclic alkyl”means an alkyl group comprising one or more carbocyclic rings of from 3to about 12 carbon atoms in size; and the term “aryl” means asubstituted or unsubstituted phenyl or naphthyl moiety. Modifiers of theform “C_(x)-C_(y)” designate that the alkyl or carbocyclic alkyl groupshave molecular formulas containing a total of x to y carbon atoms, wherex and y are specified integers. The terms “halogen-substituted”,“hydroxy-substituted”, “carboxy-substituted”,“polyoxyalkylene-substituted”, alkyl-substituted”, and“aryl-substituted” as used herein in reference to alkyl or aryl groups,and the like, mean that at least one hydrogen atom on an alkyl, aryl, orlike group has been replaced by at least one halogen atom, hydroxylgroup, carboxyl group, polyoxyalkylene group, alkyl group, or arylgroup, respectively.

[0037] Suitable monomers useful in the preparation of the multi purposeassociative polymers of the present invention are as described below.

[0038] Acidic Vinyl Monomer

[0039] Acidic vinyl monomers suitable for use in the present inventionare acidic, polymerizable, ethylenically unsaturated monomers preferablycontaining at least one carboxylic acid, sulfonic acid group, or aphosphonic acid group to provide an acidic or anionic functional site.These acid groups can be derived from monoacids or diacids, anhydridesof dicarboxylic acids, monoesters of diacids, and salts thereof.

[0040] Suitable acidic vinyl carboxylic acid-containing monomersinclude, but are not limited to: acrylic acid, methacrylic acid,itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonicacid, aconitic acid, and the like, and C₁-C₁₈ alkyl-monoesters ofmaleic, fumaric, itaconic, or aconitic acid, such as methyl hydrogenmaleate, monoisopropyl maleate, butyl hydrogen fumarate, and the like.Anhydrides of dicarboxylic acids, such as maleic anhydride, itaconicanhydride, citraconic anhydride, and the like can also be utilized asacidic vinyl monomers. Such anhydrides generally hydrolyze to thecorresponding diacids upon prolonged exposure to water, or at elevatedpH.

[0041] Suitable sulfonic acid group-containing monomers include, but arenot limited to: vinyl sulfonic acid, 2-sulfoethyl methacrylate, styrenesulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS),allyloxybenzene sulfonic acid, and the like. Particularly preferred arethe sodium salt of styrene sulfonic acid (SSSA) and AMPS.

[0042] Non-limiting examples of suitable phosphonic acidgroup-containing monomers include vinyl phosphonic acid, allylphosphonic acid, 3-acrylamidopropyl phosphonic acid, and the like.

[0043] Suitable salts include, without limitation thereto, alkali metalsalts, such as sodium, potassium and lithium salts; alkaline earth metalsalts, such as calcium and magnesium salts; ammonium salts; andalkyl-substituted ammonium salts, such as salts of2-amino-2-methyl-1-propanol (AMP), ethanolamine, diethanolamine,triethanolamine, triethylamine, and the like.

[0044] The foregoing monomers or salts thereof can be used as the acidicvinyl monomer component of the inventive ASAP, individually, or inmixtures of two or more. Acrylic acid, methacrylic acid, the sodium saltof styrene sulfonic acid (SSSA), AMPS as well as fumaric acid, maleicacid, itaconic acid, and monoesters or monoamides thereof, arepreferred. Particularly preferred acidic vinyl monomers are acrylic andmethacrylic acid, SSSA, and AMPS.

[0045] The acidic vinyl monomer preferably comprises about 10 to about75 weight percent of the total monomer mixture, more preferably about 25to about 65 weight percent, and most preferably about 30 to about 60weight percent, on a total monomer mixture weight basis.

[0046] Nonionic Monomer

[0047] Nonionic vinyl monomers suitable for use in the present inventionare copolymerizable, nonionic, ethylenically unsaturated monomers, whichare well known in the art. Preferred nonionic vinyl monomers arecompounds having either of the following formulas (I) or (II):

CH₂═C(X)Z,  (I)

CH₂═CH—OC(O)R;  (II)

[0048] wherein, in each of formulas (I) and (II), X is H or methyl; andZ is —C(O)OR¹, —C(O)NH₂, —C(O)NHR¹, —C(O)N(R¹)₂, —C₆H₄R¹, —C₆H₄OR¹,—C₆H₄Cl, —CN, —NHC(O)CH₃, —NHC(O)H, N-(2-pyrrolidonyl), N-caprolactamyl,—C(O)NHC(CH₃)₃, —C(O)NHCH₂CH₂—N-ethyleneurea, —SiR₃,—C(O)O(CH₂)_(x)SiR₃, —C(O)NH(CH₂)_(x)SiR₃, or —(CH₂)_(x)SiR₃; x is aninteger in the range of 1 to about 6; each R is independently C₁-C₁₈alkyl; each R¹ is independently C₁-C₃₀ alkyl, hydroxy-substituted C₂-C₃₀alkyl, or halogen-substituted C₁-C₃₀ alkyl.

[0049] Non-limiting examples of suitable water-insoluble, nonionic vinylmonomers include C₁-C₃₀ alkyl (meth)acrylates; C₁-C₃₀ alkyl(meth)acrylamides; styrene; substituted styrenes, such as vinyl toluene(e.g., 2-methyl styrene), butyl styrene, isopropyl styrene, p-chlorostyrene, and the like; vinyl esters, such as vinyl acetate, vinylbutyrate, vinyl caprolate, vinyl pivalate, vinyl neodecanoate, and thelike; unsaturated nitrites, such as methacrylonitrile, acrylonitrile,and the like; and unsaturated silanes, such as trimethylvinylsilane,dimethylethylvinylsilane, allyldimethylphenylsilane,allytrimethylsilane, 3-acrylamidopropyltrimethylsilane,3-trimethylsilylpropyl methacrylate, and the like.

[0050] Non-limiting examples of suitable water-soluble nonionic vinylmonomers are C₂-C₆ hydroxyalkyl (meth)acrylates; glycerolmono(meth)acrylate; tris(hydroxymethyl)ethane mono(meth)acrylate;pentaerythritol mono(meth)acrylate; N-hydroxymethyl (meth)acrylamide;2-hydroxyethyl (meth)acrylamide; 3-hydroxypropyl (meth)acrylamide;(meth)acrylamide; N-vinyl caprolactam; N-vinyl pyrrolidone;methacrylamidoethyl-N-ethyleneurea (e.g.,CH_(2═)C(CH₃)C(O)NHCH₂CH₂—N-ethyleneurea), C₁-C₄ alkoxy-substituted(meth)acrylates and (meth)acrylamides, such as methoxyethyl(meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, and the like;and combinations thereof.

[0051] Particularly preferred nonionic vinyl monomers include C₁-C₁₈alkyl esters of acrylic acid and of methacrylic acid,methacrylamidoethyl-N-ethylene urea, and combinations thereof.

[0052] The nonionic vinyl monomer preferably comprises about 10 to about90 weight percent of the total monomer mixture, more preferably about 25to about 75 weight percent, and most preferably about 30 to about 60weight percent, on a total monomer mixture weight basis.

[0053] Associative Monomer

[0054] Associative monomers suitable for the production of the inventiveASAP are compounds preferably having an ethylenically unsaturated endgroup portion (i) for addition polymerization with the other monomers ofthe system; a polyoxyalkylene midsection portion (ii) for impartingselective hydrophilic properties to the product polymer and ahydrophobic end group portion (iii) for providing selective hydrophobicproperties to the polymer.

[0055] The portion (i) supplying the ethylenically unsaturated end grouppreferably is derived from an α,β-ethylenically unsaturated mono ordi-carboxylic acid or the anhydride thereof, more preferably a C₃ or C₄mono- or di-carboxylic acid or the anhydride thereof. Alternatively,portion (i) of the associative monomer can be derived from an allylether or vinyl ether; a nonionic vinyl-substituted urethane monomer,such as disclosed in U.S. Reissue Pat. No. 33,156 or U.S. Pat. No.5,294,692; or a vinyl-substituted urea reaction product, such asdisclosed in U.S. Pat. No. 5,011,978; the relevant disclosures of eachare incorporated herein by reference.

[0056] The midsection portion (ii) is preferably a polyoxyalkylenesegment of about 5 to about 250, more preferably about 10 to about 120,and most preferably about 15 to about 60 repeating C₂-C₇ alkylene oxideunits. Preferred midsection portions (ii) include polyoxyethylene,polyoxypropylene, and polyoxybutylene segments comprising about 5 toabout 150, more preferably about 10 to about 100, and most preferablyabout 15 to about 60 ethylene, propylene or butylene oxide units, andrandom or non-random sequences of ethylene oxide, propylene oxide and orbutylene oxide units.

[0057] The hydrophobic end group portion (iii) of the associativemonomers is preferably a hydrocarbon moiety belonging to one of thefollowing hydrocarbon classes: a C₈-C₄₀ linear alkyl, anaryl-substituted C₂-C₄₀ alkyl, a C₂-C₄₀ alkyl-substituted phenyl, aC₈-C₄₀ branched alkyl, a C₈-C₄₀ carbocyclic alkyl; and a C₈-C₈₀ complexester.

[0058] As used herein and in the appended claims, the term “complexester” means a di-, tri-, or poly-ester of a polyol such as a sugar,having at least one hydroxyl group capable of being alkylated with aC₂-C₇ alkylene oxide. The term “complex ester” includes, in particular,the complex hydrophobes described by Jenkins et al. in U.S. Pat. No.5,639,841, the relevant disclosure of which is incorporated herein byreference.

[0059] Non-limiting examples of suitable hydrophobic end group portions(iii) of the associative monomers are linear or branched alkyl groupshaving about 8 to about 40 carbon atoms, such as capryl (C₈), iso-octyl(branched C₈), decyl (C₁₀), lauryl (C₁₂), myristyl (C₁₄), cetyl (C₁₆),cetearyl (C₁₆-C₁₈), stearyl (C₁₈), isostearyl (branched C₁₈), arachidyl(C₂₀), behenyl (C₂₂), lignoceryl (C₂₄), cerotyl (C₂₆), montanyl (C₂₈),melissyl (C₃₀), lacceryl (C₃₂), and the like.

[0060] Examples of linear and branched alkyl groups having about 8 toabout 40 carbon atoms that are derived from a natural source include,without being limited thereto, alkyl groups derived from hydrogenatedpeanut oil, soybean oil and canola oil (all predominately C₁₈),hydrogenated tallow oil (C₁₆-C₁₈), and the like; and hydrogenatedC₁₀-C₃₀ terpenols, such as hydrogenated geraniol (branched C₁₀),hydrogenated farnesol (branched C₁₅), hydrogenated phytol (branchedC₂₀), and the like.

[0061] Non-limiting examples of suitable C₂-C₄₀ alkyl-substituted phenylgroups include octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl,hexadecylphenyl, octadecylphenyl, isooctylphenyl, sec-butylphenyl, andthe like.

[0062] Suitable C₈-C₄₀ carbocylic alkyl groups include, without beinglimited thereto, groups derived from sterols from animal sources, suchas cholesterol, lanosterol, 7-dehydrocholesterol, and the like; fromvegetable sources, such as phytosterol, stigmasterol, campesterol, andthe like; and from yeast sources, such as ergosterol, mycosterol, andthe like. Other carbocyclic alkyl hydrophobic end groups useful in thepresent invention include, without being limited thereto, cyclooctyl,cyclododecyl, adamantyl, decahydronaphthyl, and groups derived fromnatural carbocyclic materials, such as pinene, hydrogenated retinol,camphor, isobornyl alcohol, and the like.

[0063] Exemplary aryl-substituted C₂-C₄₀ alkyl groups include, withoutlimitation thereto, styryl (e.g., 2-phenylethyl), distyryl (e.g.,2,4-diphenylbutyl), tristyryl (e.g., 2,4,6-triphenylhexyl),4-phenylbutyl, 2-methyl-2-phenylethyl, tristyrylphenolyl, and the like.

[0064] Non-limiting examples of suitable C₈-C₈₀ complex esters includehydrogenated castor oil (predominately the triglyceride of12-hydroxystearic acid); 1,2-diacyl glycerols, such as 1,2-distearylglycerol, 1,2-dipalmityl glycerol, 1,2-dimyristyl glycerol, and thelike; di-, tri-, or poly-esters of sugars, such as 3,4,6-tristearylglucose, 2,3-dilauryl fructose, and the like; and sorbitan esters, suchas those disclosed in U.S. Pat. No. 4,600,761 to Ruffner et al., thepertinent disclosures of which are incorporated herein by reference.

[0065] Useful associative monomers can be prepared by any method knownin the art. See, for example, U.S. Pat. No. 4,421,902 to Chang et al.;U.S. Pat. No. 4,384,096 to Sonnabend; U.S. Pat. No. 4,514,552 to Shay etal.; U.S. Pat. No. 4,600,761 to Ruffner et al.; U.S. Pat. No. 4,616,074to Ruffner; U.S. Pat. No. 5,294,692 to Barron et al.; U.S. Pat. No.5,292,843 to Jenkins et al.; U.S. Pat. No. 5,770,760 to Robinson; andU.S. Pat. No. 5,412,142 to Wilkerson, III et al.; the pertinentdisclosures of which are incorporated herein by reference.

[0066] Examples of preferred associative monomers include those havingformula (III).

[0067] wherein

[0068] each R² is independently H, methyl, —C(O)OH, or —C(O)OR³; R³ isC₁-C₃₀ alkyl; A is —CH₂C(O)O—, —C(O)O—, —O—, —CH₂O—, —NHC(O)NH—,—C(O)NH—, —Ar-(CE₂)_(z)—NHC(O)O—, —Ar-(CE₂)_(z)—NHC(O)NH—, or—CH₂CH₂NHC(O)—; Ar is a divalent aryl; E is H or methyl; z is 0 or 1; kis an integer in the range of 0 to about 30, and m is 0 or 1, with theproviso that when k is 0, m is 0, and when k is in the range of 1 toabout 30, m is 1; (R⁴—O)_(n) is a polyoxyalkylene, which is ahomopolymer, a random copolymer, or a block copolymer of C₂-C₄oxyalkylene units, wherein R⁴ is C₂H₄, C₃H₆, or C₄H₈, and n is aninteger in the range of about 5 to about 250, preferably about 5 toabout 100, more preferably about 10 to about 80, and most preferablyabout 15 to about 60; Y is —R⁴O—, —R⁴NH—, —C(O)—, —C(O)NH—,—R⁴NHC(O)NH—, or —C(O)NHC(O)—; R⁵ is a substituted or unsubstitutedalkyl selected from the group consisting of a C₈-C₄₀ linear alkyl, aC₈-C₄₀ branched alkyl, a C₈-C₄₀ carbocyclic alkyl, a C₂-C₄₀alkyl-substituted phenyl, an aryl-substituted C₂-C₄₀ alkyl, and a C₈-C₈₀complex ester; wherein the R⁵ alkyl group optionally comprises one ormore substituents selected from the group consisting of a hydroxylgroup, an alkoxyl group, and a halogen group.

[0069] Particularly preferred associative monomers of formula (III)include cetyl polyethoxylated methacrylate (CEM), cetearylpolyethoxylated methacrylate (CSEM), stearyl polyethoxylated(meth)acrylate, arachidyl polyethoxylated (meth)acrylate, behenylpolyethoxylated methacrylate (BEM), cerotyl polyethoxylated(meth)acrylate, montanyl polyethoxylated (meth)acrylate, melissylpolyethoxylated (meth)acrylate, lacceryl polyethoxylated (meth)acrylate,tristyrylphenol polyethoxylated methacrylate (TEM), hydrogenated castoroil polyethoxylated methacrylate (HCOEM), canola polyethoxylated(meth)acrylate, and cholesterol polyethoxylated methacrylate (CHEM),where the polyethoxylated portion of the monomer comprises about 5 toabout 100, preferably about 10 to about 80, and more preferably about 15to about 60 ethylene oxide repeating units.

[0070] Preferably, the associative monomer components in the monomermixture independently comprise, on a total monomer mixture weight basis,about 0.1 to about 25 weight percent of the monomer mixture, morepreferably about 0.25 to about 20 weight percent, most preferably about0.5 to about 15 weight percent.

[0071] Semihydrophobic Monomer

[0072] It was surprisingly found that a semihydrophobic monomer (SHmonomer) can moderate the associative properties of polymers containingthem, thus producing aqueous gels with highly desirable texture andrheological properties. Not wishing to be bound by theory, it is thoughtthat the polyoxyalkylene group of the SH monomer interrupts or shieldsagainst non-specific associations between the hydrophobic groups of theassociative monomers in the polymer, or external components and thusattenuates the associative properties of the polymers. Such SH monomerscan tailor the thickening efficiency of the resulting polymers tocustomize the rheological properties of the polymer as desired for aselected application. Most surprisingly, alkali-swellable polymerscontaining the SH monomers were found to impart desirable rheologicaland aesthetic properties to aqueous gels, generally providing softer,smoother and more spreadable gels at all polymer concentrations than didalkali-swellable associative polymers containing no SH monomer andprovided a Brookfield viscosity that remained substantially unchangedover a period of 24 hours.

[0073] Surprisingly, incorporation of a SH monomer into analkali-swellable associative polymer can reduce gel viscosity at lowshear stress, minimize or eliminate viscosity reduction as shear stressis increased and minimize or decrease shear thinning behavior of thegels. For example, Polymer CP-5, described in Example 1 below, having 3%BEM25 associative monomer, when measured by a complex viscositytechnique at an active polymer weight concentration of about 1.2%, had aviscosity of 178 Pa·s (178,000 cP) at a shear stress of 1 Pa; andincreasing the shear stress to 5 Pa led to a reduction in complexviscosity to 43.6 Pa·s. Adding a SH monomer to the polymer, e.g. as inPolymer AG, Example 1, which has 3% BEM25 and 5% of the SH monomer R307,had two effects. First, the complex viscosity measured at an activepolymer weight concentration of about 1.2% at 1 Pa shear stress wasreduced to 106 Pa·s. Second, upon increasing the shear stress to 5 Pa,the complex viscosity measurement remained almost unchanged (105.5Pa·s). Similarly, when 15% of SH monomer was incorporated (e.g., as inPolymer AI, Example 1), the complex viscosity measured at an activepolymer weight concentration of about 1.2% at 1 Pa shear stress was 46.5Pa·s, whereas at 5 Pa shear stress the complex viscosity measured was 36Pa·s.

[0074] As used herein and in the appended claims, the termssemihydrophobic monomer” and “SH monomers” refer to compounds having twoportions: (i) an ethylenically unsaturated end group portion foraddition polymerization with the other monomers of the reaction mixture,and (ii) a polyoxyalkylene portion for attenuating the associationsbetween the hydrophobic groups of the polymer or hydrophobic groups fromother materials in a composition containing the polymer. Asemihydrophobic monomer is similar to an associative monomer, but has asubstantially non-hydrophobic end group portion.

[0075] The unsaturated end group-portion (i) supplying the vinyl orother ethylenically unsaturated end group for addition polymerization ispreferably derived from an α,β-ethylenically unsaturated mono ordi-carboxylic acid or the anhydride thereof, preferably a C₃ or C₄ mono-or di-carboxylic acid, or the anhydride thereof. Alternatively, the endgroup portion (i) can be derived from an allyl ether, a vinyl ether or anonionic urethane monomer.

[0076] The polymerizable unsaturated end group portion (i) can also bederived from a C₈-C₃₀ unsaturated fatty acid group containing at leastone free carboxy-functional group. This C₈-C₃₀ group is part of theunsaturated end group portion (i) and is different from the hydrophobicgroups pendant to the associative monomers, which are specificallyseparated from the unsaturated end group of the associative monomer by ahydrophilic “spacer” portion.

[0077] The polyoxyalkylene portion (ii) specifically comprises along-chain polyoxyalkylene segment, which is substantially similar tothe hydrophilic portion of the associative monomers. Preferredpolyoxyalkylene portions (ii) include polyoxyethylene, polyoxypropylene,and polyoxybutylene units comprising about 2 to about 250, andpreferably about 10 to about 100 ethylene oxide, propylene oxide, orbutylene oxide units, or random or non-random sequences of ethyleneoxide, propylene oxide, and/or butylene oxide units.

[0078] Preferred SH monomers include those having either of thefollowing formulas (IV) or (V):

[0079] wherein, in each of formulas (IV) and (V),

[0080] each R⁶ is independently H, C₁-C₃₀ alkyl, —C(O)OH, or —C(O)OR⁷;R⁷ is C₁-C₃₀ alkyl; A is —CH₂C(O)O—, —C(O)O—, —O—, —CH₂O—, —NHC(O)NH—,—C(O)NH—, —Ar-(CE₂)_(z)—NHC(O)O—, —Ar-(CE₂)_(z)—NHC(O)NH—, or—CH₂CH₂NHC(O)—; Ar is a divalent aryl; E is H or methyl; z is 0 or 1; pis an integer in the range of 0 to about 30, and r is 0 or 1, with theproviso that when p is 0, r is 0, and when p is in the range of 1 toabout 30, r is 1; (R⁸—O) is a polyoxyalkylene, which is a homopolymer, arandom copolymer, or a block copolymer of C₂-C₄ oxyalkylene units,wherein R⁸ is C₂H₄, C₃H₆, or a mixture thereof, and v is an integer inthe range of about 5 to about 250, preferably about 5 to about 100, morepreferably about 10 to about 80, and most preferably about 15 to about60; R⁹ is H or C₁-C₄ alkyl; and D is a C₈-C₃₀ unsaturated alkyl or acarboxy-substituted C₈-C₃₀ unsaturated alkyl.

[0081] Particularly preferred semihydrophobic monomers include monomershaving the following chemical formulas:

CH₂═CH—O—(CH₂)_(z)—O—(C₃H₆O)_(b)—(C₂H₄O)_(c)—H or

CH₂═CH—CH₂—O—(C₃H₆O)_(d)—(C₂H₄O)_(e)—H;

[0082] wherein a, preferably, is 2, 3, or 4; b, preferably, is aninteger in the range of 1 to about 10, more preferably about 2 to about8, most preferably about 3 to about 7; c, preferably, is an integer inthe range of about 5-to about 50, more preferably about 8 to about 40,most preferably about 10 to about 30; d, preferably, is an integer inthe range of 1 to about 10, more preferably about 2 to about 8, mostpreferably about 3 to about 7; and e, preferably, is an integer in therange of about 5 to about 50, more preferably about 8 to about 40.

[0083] Examples of preferred SH monomers include polymerizableemulsifiers commercially available under the trade names EMULSOGEN®R109, R208, R307, RAL109, RAL208, and RAL307 sold by ClariantCorporation; BX-AA-E5P5 sold by Bimax, Inc.; and MAXEMUL® 5010 and 5011sold by Uniqema; and combinations thereof. Particularly preferred SHmonomers include EMULSOGEN® R109, R208, and R307, BX-AA-E5P5, MAXEMUL®5010 and 5011, and combinations thereof.

[0084] According to the manufacturers: EMULSOGEN® R109 is a randomlyethoxylated/propoxylated 1,4-butanediol vinyl ether having the empiricalformula CH₂═CH—O(CH₂)₄O(C₃H₆O)₄(C₂H₄O)₁₀H; EMULSOGEN® R208 is a randomlyethoxylated/propoxylated 1,4-butanediol vinyl ether having the empiricalformula CH₂═CH—O(CH₂)₄O(C₃H₆O)₄(C₂H₄O)₂₀H; EMULSOGEN® R307 is a randomlyethoxylated/propoxylated 1,4-butanediol vinyl ether having the empiricalformula CH₂═CH—O(CH₂)₄O(C₃H₆O)₄(C₂H₄O)₃₀H; EMULSOGEN® RAL109 is arandomly ethoxylated/propoxylated allyl ether having the empiricalformula CH₂═CHCH₂O(C₃H₆O)₄(C₂H₄O)₁₀H; EMULSOGEN® RAL208 is a randomlyethoxylated/propoxylated allyl ether having the empirical formulaCH_(2═)CHCH₂O(C₃H₆O)₄(C₂H₄O)₂₀H; EMULSOGEN® RAL307 is a randomlyethoxylated/propoxylated allyl ether having the empirical formulaCH₂═CHCH₂O(C₃H₆O)₄(C₂H₄O)₃₀H; MAXEMUL® 5010 is a carboxy-functionalC₁₂-C₁₅ alkenyl hydrophobe, ethoxylated with about 24 ethylene oxideunits; MAXEMUL® 5011 is a carboxy-functional C₁₂-C₁₅ alkenyl hydrophobe,ethoxylated with about 34 ethylene oxide units; and BX-AA-E5P5 is arandomly ethoxylated/propoxylated allyl ether having the empiricalformula CH₂═CHCH₂O(C₃H₆O)₅(C₂H₄O)₅H.

[0085] The amount of semihydrophobic monomers utilized in thepreparation of the polymers of the present invention can vary widely anddepends, among other things, on the final rheological and aestheticproperties desired in the polymer. When utilized, the monomer reactionmixture preferably contains one or more semihydrophobic monomers inamounts in the range of about 0.1 to about 25 weight percent based onthe total monomer mixture weight, more preferably about 0.5 to about 20weight percent, most preferably about 1 to about 15 weight percent.

[0086] Crosslinking Monomer

[0087] The ASAP can optionally be prepared from a monomer mixturecomprising one or more crosslinking monomer for introducing branchingand controlling molecular weight. Suitable polyunsaturated crosslinkersare well known in the art. Mono-unsaturated compounds carrying areactive group that is capable of causing a formed copolymer to becrosslinked before, during, or after polymerization has taken place canalso be utilized. Other useful crosslinking monomers includepolyfunctional monomers containing multiple reactive groups, such asepoxide groups, isocyanate groups, and hydrolyzable silane groups.Various polyunsaturated compounds can be utilized to generate either apartially or substantially cross-linked three dimensional network.

[0088] Examples of suitable polyunsaturated crosslinking monomercomponents include, without being limited thereto, polyunsaturatedaromatic monomers, such as divinylbenzene, divinyl naphthalene, andtrivinylbenzene; polyunsaturated alicyclic monomers, such as1,2,4-trivinylcyclohexane; di-functional esters of phthalic acid, suchas diallyl phthalate; polyunsaturated aliphatic monomers, such asdienes, trienes, and tetraenes, including isoprene, butadiene,1,5-hexadiene, 1,5,9-decatriene, 1,9-decadiene, 1,5-heptadiene; and thelike.

[0089] Other suitable polyunsaturated crosslinking monomers includepolyalkenyl ethers, such as triallyl pentaerythritol, diallylpentaerythritol, diallyl sucrose, octaallyl sucrose, andtrimethylolpropane diallyl ether; polyunsaturated esters of polyalcoholsor polyacids, such as 1,6-hexanediol di(meth)acrylate, tetramethylenetri(meth)acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate,diallyl maleate, trimethylolpropane tri(meth)acrylate,trimethylolpropane di(meth)acrylate, and polyethylene glycoldi(meth)acrylate; alkylene bisacrylamides, such as methylenebisacrylamide, propylene bisacrylamide, and the like; hydroxy andcarboxy derivatives of methylene bis-acrylamide, such asN,N′-bismethylol methylene bisacrylamide; polyethyleneglycoldi(meth)acrylates, such as ethyleneglycol di(meth)acrylate,diethyleneglycol di(meth)acrylate, and triethyleneglycoldi(meth)acrylate; polyunsaturated silanes, such asdimethyldivinylsilane, methyltrivinylsilane, allyldimethylvinylsilane,diallydimethylsilane and tetravinylsilane; polyunsaturated stannanes,such as tetraallyl tin, diallyldimethyl tin; and the like.

[0090] Useful monounsaturated compounds carrying a reactive groupinclude N-methylolacrylamide; N-alkoxy(meth)acrylamide, wherein thealkoxy group is a C₁-C₁₈ alkoxy; and unsaturated hydrolyzable silanes,such as triethoxyvinylsilane, tris-isopropoxyvinylsilane,3-triethoxysilylpropyl methacrylate, and the like.

[0091] Useful polyfunctional crosslinking monomers containing multiplereactive groups include, but are not limited to, hydrolyzable silanes,such as ethyltriethoxysilane and ethyltrimethoxysilane,epoxy-substituted hydrolyzable silanes, such as2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and3-glycidoxypropyltrimethyoxysilane; polyisocyanates, such as1,4-diisocyanatobutane, 1,6-diisocyanatohexane,1,4-phenylenediisocyanate and 4,4′-oxybis(phenylisocyanate); unsaturatedepoxides, such as glycidyl methacrylate and allylglycidyl ether;polyepoxides, such as diglycidyl ether, 1,2,5,6-diepoxyhexane, andethyleneglycoldiglycidyl ether; and the like.

[0092] Particularly useful are polyunsaturated crosslinkers derived fromethoxylated polyols, such as diols, triols and bis-phenols, ethoxylatedwith about 2 to about 100 moles of ethylene oxide per mole of hydroxylfunctional group and end-capped with a polymerizable unsaturated group,such as a vinyl ether, allyl ether, acrylate ester, methacrylate ester,and the like. Examples of such crosslinkers include bisphenol Aethoxylated dimethacrylate; bisphenol F ethoxylated dimethacrylate,trimethylol propane ethoxylated trimethacrylate, and the like. Otherethoxylated crosslinkers useful in the ASAP polymers of the presentinvention include ethoxylated polyol-derived crosslinkers disclosed inU.S. Pat. No. 6,140,435 to Zanotti-Russo, the pertinent disclosures ofwhich are incorporated herein by reference.

[0093] Examples of particularly preferred crosslinkers are acrylate andmethacrylate esters of polyols having at least two acrylate ormethacrylate ester groups, such as trimethylolpropane triacrylate(TMPTA), trimethylolpropane dimethacrylate, polyethylene glycoldimethacrylate, ethoxylated (30) bisphenol A dimethacrylate (EOBDMA),and the like.

[0094] When utilized, crosslinking monomers are present in the monomerreaction mixture preferably in an amount in the range of about 0.01 toabout 2 weight percent, based on the total monomer mixture weight, morepreferably about 0.05 to about 1.5 weight percent, most preferably about0.1 to about 1 weight percent of the monomer mixture.

[0095] Chain Transfer Agent

[0096] The ASAP of the present invention can optionally be prepared froma monomer mixture comprising one or more chain transfer agents, whichare well known in the polymer arts.

[0097] Suitable chain transfer agents for use in this invention, withoutbeing limited thereto, are selected from a variety of thio and disulfidecontaining compounds, such as C₁-C₁₈ alkyl mercaptans,mercaptocarboxylic acids, mercaptocarboxylic esters, thioesters, C₁-C₁₈alkyl disulfides, aryldisulfides, polyfunctional thiols, and the like;phosphites and hypophosphites; haloalkyl compounds, such as carbontetrachloride, bromotrichloromethane, and the like; and unsaturatedchain transfer agents, such as alpha-methylstyrene.

[0098] Polyfunctional thiols include trifunctional thiols, such astrimethylolpropane-tris-(3-mercaptopropionate), tetrafunctional thiols,such as pentaerythritol-tetra-(3-mercaptopropionate),pentaerythritol-tetra-(thioglycolate), andpentaerythritol-tetra-(thiolactate); hexafunctional thiols, such asdipentaerythritol-hexa-(thioglycolate); and the like.

[0099] Alternatively, the chain transfer agent can be any catalyticchain transfer agent which reduces molecular weight of addition polymersduring free radical polymerization of vinyl monomers. Examples ofcatalytic chain transfer agents include, for example, cobalt complexes(e.g., cobalt (II) chelates). Catalytic chain transfer agents can oftenbe utilized in relatively low concentrations relative to thiol-basedCTAs.

[0100] Examples of preferred chain transfer agents include octylmercaptan, n-dodecyl mercaptan (DDM), t-dodecyl mercaptan, hexadecylmercaptan, octadecyl mercaptan (ODM), isooctyl 3-mercaptopropionate(IMP), butyl 3-mercaptopropionate, 3-mercaptopropionic acid, butylthioglycolate, isooctyl thioglycolate, dodecyl thioglycolate, and thelike. The chain transfer agents can be added to a monomer reactionmixture preferably in amounts of up to about 10 weight percent ofpolymerizable monomer mixture, based on total monomer mixture weight.

[0101] The inventive ASAP can be manufactured by conventionalpolymerization techniques, such as emulsion polymerization, as is knownin the polymer art. Typically the polymerization process is carried outat a reaction temperature in the range of about 30 to about 95° C.,however, higher or lower temperatures can be used. To facilitateemulsification of the monomer mixture, the emulsion polymerization canbe carried out in the presence of anionic surfactants, such as fattyalcohol sulfates or alkyl sulfonates, nonionic surfactants, such aslinear or branched alcohol ethoxylates, amphoteric surfactants, ormixtures thereof. The emulsion polymerization reaction mixture alsoincludes one or more free radical initiators, preferably in an amount inthe range of about 0.01 to about 3 weight percent based on total monomerweight. The polymerization can be performed in an aqueous or aqueousalcohol medium at a low pH, i.e., preferably not more than about pH 4.5.

[0102] Anionic surfactants suitable for facilitating emulsionpolymerizations are well known in the polymer art, and include sodiumlauryl sulfate, sodium dodecyl benzene sulfonate, disodium laureth-3sulfosuccinate, sodium dioctyl sulfosuccinate, sodium di-sec-butylnaphthalene sulfonate, disodium dodecyl diphenyl ether sulfonate,disodium n-octadecyl sulfosuccinate, phosphate esters of branchedalcohol ethoxylates, and the like.

[0103] Exemplary free radical initiators include, without being limitedthereto, the water-soluble inorganic persulfate compounds, such asammonium persulfate, potassium persulfate, and sodium persulfate;peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide,and lauryl peroxide; organic hydroperoxides, such as cumenehydroperoxide and t-butyl hydroperoxide; organic peracids, such asperacetic acid and perbenzoic acid (optionally activated with reducingagents, such as sodium bisulfite or ascorbic acid); and oil soluble,free radical producing agents, such as 2,2′-azobisisobutyronitrile, andthe like. Particularly suitable free-radical polymerization initiatorsinclude water soluble azo polymerization initiators, such as2,2′-azobis(tert-alkyl) compounds having a water solubilizingsubstituent on the alkyl group. Preferred azo polymerization catalystsinclude the VAZO® free-radical polymerization initiators, available fromDuPont, such as VAZO® 44 (2,2′-azobis(2-(4,5-dihydroimidazolyl)propane),VAZO® 56 (2,2′-azobis(2-methylpropionamidine) dihydrochloride), andVAZO® 68 (4,4′-azobis(4-cyanovaleric acid)).

[0104] Optionally, other emulsion polymerization additives, which arewell known in the emulsion polymerization art, such as buffering agents,chelating agents, inorganic electrolytes, chain terminators, and pHadjusting agents can be included in the polymerization system.

[0105] A preferred general emulsion polymerization procedure for thepreparation of alkali-swellable or alkali-soluble associated polymers ofthe present invention is provided below:

[0106] A monomer emulsion is prepared in a first reactor equipped with anitrogen inlet and an agitator, by combining a desired amount of eachmonomer in water containing an emulsifying amount of an anionicsurfactant under a nitrogen atmosphere and with mixing agitation. To asecond reactor equipped with an agitator, nitrogen inlet and feed pumps,are added a desired amount of water and additional anionic surfactant,if desired, under a nitrogen atmosphere, and the contents of the secondreactor are heated with mixing agitation. After the contents of thesecond reactor reach a temperature in the range of about 65-98° C., afree radical initiator is injected into the so-formed aqueous surfactantsolution in the second reactor, and the monomer emulsion from the firstreactor is then gradually pumped into the second reactor over a periodof typically in the range of about one to about four hours at acontrolled reaction temperature in the range of about 65-95° C. Aftercompletion of the monomer addition, an additional quantity of freeradical initiator can be added to the second reactor, if desired, andthe resulting reaction mixture is typically held at a temperature ofabout 75-95° C. for a time period sufficient to complete thepolymerization reaction. The resulting polymer emulsion can then becooled and discharged from the reactor.

[0107] One skilled in the polymer arts will recognize that the amountsof each monomer component can be adjusted to obtain polymers having anydesired ratio of monomers. Larger or smaller proportions of water mayalso be utilized, as desired. Water miscible solvents, such as alcohols,and other polymerization additives, as described above, may also beincluded in the reaction mixture. Nonionic surfactants, such as linearor branched alcohol ethoxylates, can also be added as is known in theemulsion polymerization art.

[0108] The product polymer emulsions can be prepared to preferablycontain about 1 percent to about 60 percent total polymer solids, morepreferably about 10 percent to about 50 percent total polymer solids,most preferably about 15 percent to about 45 percent total polymersolids (TS) based on the weight of the polymer.

[0109] Prior to any neutralization, the polymer emulsions, as produced,typically have a pH in the range of about 2 to not more than about 5.5,a Brookfield viscosity of not more than about 100 milli-Pascal seconds(mPa·s) at ambient room temperature (spindle #2, 20 rpm) and a glasstransition temperature (Tg) of not more than about 150° C. as determinedby Method C below.

[0110] Optionally, the produced polymer emulsions can be furtherprocessed by adjusting the pH to a value preferably in the range ofabout 3 to about 7.5 or greater, if an alkaline pH is desired, withalkaline materials, preferably alkali metal hydroxides, organic bases,and the like. The polymer emulsions typically swell to a viscositygreater than about 100 mPa·s and form viscous solutions or gels atneutral to alkaline pH, and the polymers are generally substantiallystable at such pH values, even at pH values greater than about 12. Thepolymer emulsions can be diluted with water or solvent, or concentratedby evaporation of a portion of the water. Alternatively, the obtainedpolymer emulsion may be substantially dried to a powder or crystallineform by utilizing equipment well known in the art, such as, for example,a spray drier, a drum drier, or a freeze drier.

[0111] The inventive ASAP can be prepared by emulsion polymerization andutilized by incorporating various known additives and conventionaladjuvants, and solvents other than water, into the ASAP emulsionproduct, as needed, to achieve the intended form for use of the finalcomposition without altering or adversely affecting the performance orproperties of the ASAP. Alternatively, the ASAP can be incorporated asan ingredient into a formulation, preferably in a liquid form, employingconventional mixing equipment.

[0112] The ASAP of this invention can be employed as a film former. Whenthe glass transition temperature (Tg) of a selected ASAP film former issubstantially above ambient room temperature, the Tg of the ASAP filmformer can be adjusted to achieve a desired Tg by including additives inthe formulation, such as coalescing agents, plasticizers and mixturesthereof. Such additives can assist in film formation by lowering the Tgof the ASAP to the ambient room temperature or desired temperature.

[0113] The inventive ASAP can be utilized, for example, without beinglimited thereto, as a rheology modifier, suspending agent, film former,thickener, stabilizer, emulsifier, solubilizer, and the like, informulated compositions for personal care products, topical health careproducts, household care products, institutional and industrial (I&I)products and industrial processes. The foregoing products can typicallycontain various additives and conventional adjuvants as are well knownin the art, including, without being limited thereto, acidifying oralkalizing pH adjusting agents and buffering agents; fixatives and filmformers, such as gums, resins, polymers of synthetic or natural origin,and the like; auxiliary rheology modifiers, such as viscosity-increasingpolymeric thickeners or gellants, additives, such as emulsifiers,emulsion stabilizers, waxes, dispersants, and the like, and viscositycontrol agents, such as solvents, electrolytes, and the like; hair andskin conditioning agents, such as antistatic agents, synthetic oils,vegetable or animal oils, silicone oils, monomeric or polymericquaternized ammonium salts, emollients, humectants, lubricants,sunscreen agents, and the like; chemical hair waving or straighteningagents; hair colorants, such as pigments and dyes for temporary,semipermanent, or permanent hair dyeing; surfactants, such as anionic,cationic, nonionic, amphoteric and zwitterionic surfactants; polymerfilm modifying agents, such as plasticizers, humectants, tackifiers,detackifiers, wetting agents and the like, product finishing agents,such as chelating agents, opacifiers, pearlescing agents, preservatives,fragrances, solubilizers, colorants, such as pigments and dyes, UVabsorbers, and the like; propellants (water-miscible orwater-immiscible), such as fluorinated hydrocarbons, liquid volatilehydrocarbons, compressed gases, and the like; and mixtures thereof.

[0114] In one preferred embodiment, an aqueous gel formulationcomprising an ASAP of the present invention also includes a C₁-C₈monohydric alcohol such as methanol, ethanol, isopropanol, hexanol,benzyl alcohol, and the like, or a C₃-C₈ polyol such as ethylene glycol,propylene glycol, glycerin, hexylene glycol, butylene glycol, inositol,sorbitol, mannitol, and the like. The amount of ASAP employed is notlimited, as long as the purpose and properties of the compositionscontaining the ASAP perform their intended function. A useful amount ofactive weight percent ASAP can be in the range of about 0.01% to about25%, preferably about 0.05% to about 20%; more preferably about 0.1% toabout 15%.

[0115] In a preferred alkali-swellable ASAP embodiment, a concentrationof about 1 active weight % ASAP in deionized water, in its neutralizedor anionic form at a pH in the range of about 3 to about 9, can providea Brookfield viscosity ranging from about 100 mPa·s to 100,000 mPa·s ormore (Brookfield RVT, 20 rpm, at about 25° C. ambient room temperature).In a preferred alkali-soluble ASAP embodiment, a concentration of about5 active weight % ASAP in deionized water or in a hydroalcoholic medium,in its neutralized form at a pH in the range of about 5.5 to about 8.5provides a Brookfield viscosity preferably of not more than about 1000mPa·s.

[0116] While the ASAP minimize or eliminate the need for addedthickeners, the ASAP can be used in combination with conventionalpolymeric thickeners, such as natural gums, resins, polysaccharides,synthetic polymeric thickeners, and the like, popularly used in the art.It is known that the viscosity obtained with anionic polymers, such asalkali-swellable carbomer polymer, commonly employed as a thickener oras a drug carrier in medicaments, can be negatively affected by thepresence of anionic polymer. Surprisingly, it was found that the ASAPwere compatible with either traditional carbomer polymer or withhydrophobically-modified carbomer polymer and the viscosity produced bysuch combinations was unexpectedly higher than the sum of theviscosities of alkali-swellable ASAP and carbomer polymer by themselvesat the same concentrations. This beneficially allows the use ofalkali-swellable ASAP in formulations containing carbomer polymer orhydrophobically modified carbomer polymer, if desired, to furtherenhance the aesthetic and rheological properties of the formulation.

[0117] Concentrated additives, adjuvant ingredients, products ormaterials that can be employed with the inventive polymers are referredto herein by the international nomenclature commonly known to as INCIname given them in the International Cosmetic Ingredient Dictionary,Volumes 1 and 2, Sixth Edition, (1995), or International CosmeticIngredient Dictionary and Handbook, Volumes 1-3, Seventh Edition,(1997), both published by the Cosmetic, Toiletry, and FragranceAssociation, Washington D.C. (both hereafter INCI Dictionary), or bytheir commonly used chemical names. Numerous commercial suppliers ofmaterials that can be employed, listed by INCI name, trade name or bothcan be found in the INCI Dictionary and in numerous commercial tradepublications, including but not limited to the 2001 McCutcheon'sDirectories, Volume 1: Emulsifiers & Detergents and Volume 2: FunctionalMaterials, published by McCutcheon's Division, The ManufacturingConfectioner Publishing Co. Glen Rock, N.J. (2001); and 2001 CosmeticBench Reference, edition of COSMETICS & TOILETRIES®, 115 (13), publishedby Allured Publishing Corporation, Carol Stream, Ill. (2001); therelevant disclosures of the INCI Dictionary and each of the foregoingpublications being incorporated herein by reference.

[0118] Compositions for personal care and topical health care cancomprise any cosmetic, toiletry, and topical pharmaceutical formulationthat requires rheology modification or thickening known from thecosmetic and pharmaceutical literature. Typical personal careformulations that can include the ASAP as a rheology modifier include,without being limited thereto, shampoos, chemical and non-chemical haircurling and hair straightening products, hair style maintenanceproducts, emulsion lotions and creams for the nails, hands, feet, face,scalp, and body, hair dyes, face and body makeup, nail care products,astringents, deodorants, antiperspirants, depilatories, skin-protectivecreams and lotions, such as sunscreens, skin and body cleansers, skinconditioners, skin toners, skin firming compositions, liquid soaps, soapbars, bath products, shaving products, and the like. Formulatedcompositions for topical health care that are applied to the skin andmucous membranes for cleansing or soothing are compounded with many ofthe same physiologically tolerable cosmetic ingredients and chemicallyinert ingredients employed for personal care products in the sameproduct forms, differing primarily in the purity grade of ingredientsand by the presence of topically active medicaments. For example,topical health care products include oral hygiene products, such astoothpastes, oral suspensions, and mouth care products, which can beclassified as pharmaceuticals or over-the-counter products, and includepharmacosmetics, which contain phytopharmaceutic or nutraceuticalingredients.

[0119] Compositions for personal care and topical health care can be inthe form of, without being limited thereto, liquids, such as rinses,gels, sprays, emulsions, such as lotions and creams, shampoos, pomades,foams, ointments, tablets, sticks, such as lip care products, makeup,and suppositories, and like products, which are applied to skin and hairand remain in contact therewith until removed as by rinsing with wateror washing with shampoo or soap. Gels can be soft, stiff, or squeezable.Emulsions can be oil-in-water, water-in-oil, or multiphase. Sprays canbe non-pressurized aerosols delivered from manually pumpedfinger-actuated sprayers or can be pressurized aerosols. The ASAP can beformulated in an aerosol composition, such as in a spray, mousse, orfoam forming formulation, where a chemical or gaseous propellant isrequired. Physiologically and environmentally tolerable propellants,such as compressed gases, fluorinated hydrocarbons and liquid volatilehydrocarbons, and the amounts and suitable combinations to be used, arewell known in the cosmetic and pharmaceutical art and literature.

[0120] An extensive listing of personal care and cosmetic ingredientsand their functions, for example, appears in the INCI Dictionary,generally, and in Vol. 2, Section 4 of the Seventh Edition, inparticular, incorporated herein by reference. Those skilled in the artof formulating personal care and health care products recognize thatsome ingredients are multifunctional and, hence, can serve more than onepurpose in the formulation. Thus, the amount of ASAP polymer employed asa personal care or health care product component is not limited, as longas the purpose and properties of the formulated composition performs itsintended function.

[0121] Typical household care, and I&I care products that can containASAP as a rheology modifier include, without being limited thereto,surface cleansers for kitchen and bathroom counter tops, tiled surfaces,and utilities, including appliances employed or located therein, toiletcleaners, including toilet bowl rim gels, floor cleansers, wallcleansers, polishes, air freshener gels, detergents, treatments andcleansers for dishes and laundry, such as fabric softener, spot reducer,fabric treatments, and the like.

[0122] The ASAP are suitable for use as rheology modifiers in industrialprocesses and applications. For example, the ASAP can be employed intextile treatments as processing and finishing aids for textile coating,printing and finishing formulations, inks, metal cleaners, scaleremovers, paint and varnish strippers, polishes for furniture, shoes,cars, or metal, and the like.

[0123] Thus, compositions containing ASAP can be in any form, includingbut not limited to, a liquid, a gel, a spray, an emulsion, a semisolid,such as a paste, a solid, such as a stick, tablet or bar, and the like,so long as the composition is useful for its intended function.

[0124] The following examples further illustrate the preparation and useof preferred embodiments but are not intended to be limiting.

Materials and Procedures

[0125] The materials are generally commercially available from chemicalsupply houses known to those skilled in the chemical arts or from thesupplier indicated.

[0126] 1. Materials Abbreviations and Trade Names EA Ethyl acrylate WAMMethacrylamidoethyl-N-ethyleneurea (SIPOMER ® WAM II, Rhodia, Inc.) MAAMethacrylic acid MMA Methyl methacrylate AA Acrylic acid SSSA Sodiumsalt of styrene sulfonic acid BEM25 Beheneth-25 methacrylate LEM23Laureth-23 methacrylate CSEM25 Ceteareth-25 methacrylate HCOEM25Hydrogenated castor oil ethoxylated (25) methacrylate HCOEM16Hydrogenated castor oil ethoxylated (16) methacrylate TEM25Tristyrylphenol ethoxylated (25) methacrylate CHEM24 Choleth-24methacrylate CEM24 Ceteth-24 methacrylate EOBDMA Ethoxylated (30)bisphenol A dimethacrylate TMPTA Trimethylolpropane triacrylate IMPIsooctyl 3-mercaptopropionate DDM Dodecyl mercaptan ODM Octadecylmercaptan R307 A randomly ethoxylated/propoxylated 1,4-butanediol vinylether having the empirical formulaCH₂═CH—O—(CH₂)₄—O—(C₃H₆O)₄—(C₂H₄O)₃₀—H (EMULSOGEN ® R307, ClariantCorporation) BX-AA A randomly ethoxylated/propoxylated allyl etherhaving the empirical formula CH₂═CH—CH₂—O—(C₃H₆O)₅—(C₂H₄O)₅—H(BX-AA-E5P5, Bimax, Inc.) M5010 A carboxy-functional C₁₂-C₁₅ alkenylhydrophobe, ethoxylated with about 24 ethylene oxide units (MAXEMUL ®5010, Uniqema) MPEG35 Methoxy ethoxylated (35) methacrylate MPEG55Methoxy ethoxylated (55) methacrylate

[0127] 2. Methods.

[0128] A. Viscosity. The reported viscosity of each polymer containingcomposition was measured in milli-Pascal seconds (mPa·s), employing aBrookfield rotating spindle viscometer, (Brookfield, Model RVT) at about20 revolutions per minute (rpm), at ambient room temperature of about20-25° C. (hereafter referred to as Brookfield viscosity). Viscosity wasmeasured on freshly prepared compositions (referred to as “initialviscosity”, and re-measured after allowing the composition to age for atleast about 24 hours at ambient room temperature (referred to as“24-hour viscosity”). Where only one viscosity value is shown below, theviscosity value is the 24-hour viscosity, unless otherwise indicated.

[0129] A “thin viscosity” typically refers to a pourable, runny,sprayable, product having a viscosity of up to about 1,000 mPa·s; a“medium viscosity” refers to a product having a viscosity in the rangeof above 1,000 to about 3,000 mPa·s; a “high viscosity” refers to aproduct having a viscosity in the range of above 3,000 to about 10,000mPa·s; and gel refers to a product having a viscosity greater than10,000 mPa·s, unless otherwise indicated.

[0130] B. Clarity. When reported, the clarity of the polymer-containingcomposition was measured in % T (transmittance) by Brinkmann PC 920calorimeter at least about 24 hours after the composition was made.Clarity measurements were taken against deionized water (clarity ratingof 100%). Compositions having a clarity of about 60% or more weresubstantially clear; compositions having a clarity in the range of about45-59% were judged substantially translucent.

[0131] C. Glass transition temperature. When reported, the glasstransition temperature (Tg) of the associative polymer was determined bycasting a portion of the product emulsion on a MYLAR® (polyethyleneterephthalate) film substrate using a 10 mil opening draw-down bar,drying the cast film at ambient room temperature (about 25° C.) forabout 24 hours, and then measuring the T_(g) by well known DifferentialScanning Calorimetry (DSC) technique.

[0132] D. Gloss. When reported, the gloss of the associative polymerfilm was determined by casting a film of the polymer product on a LenetaForm 2C-opacity chart (Leneta Co.) using a 10 mil opening draw down bar,drying the cast film at about 25° C. (about 77° F.) for about 24 hours,and then instrumentally measuring the specular gloss of the dried filmat a reflectance angle of 20° and 60° geometry employing aMicro-Tri-Gloss glossmeter, (Byk/Gardner, Silver Spring, Md.) using theStandard Test Method for Specular Gloss, ASTM 523-89 (Reapproved 1994).A specular gloss value of 100 units was assigned to the standard foreach geometry. A specular gloss value unit reading of at least about 30at an angle of 20° and at least about 80 at an angle of 60° was judgedglossy and a value of less than 25 at either angle was judged dull.

[0133] E. Turbidity. When reported, the turbidity of apolymer-containing composition was determined in Nephelometric TurbidityUnits (NTU) employing a nephelometric turbidity meter with distilledwater (NTU=0) as the standard. Compositions having an NTU value of about90 or greater were judged turbid.

[0134] F. Humidity Resistance—Percent curl retention. The resistance ofa polymer to high humidity (about 90% Relative Humidity (RH)) wasmeasured by its ability to hold a curl set on hair after absorption ofwater from the applied composition and from the surrounding atmosphereemploying the well known technique commonly referred to as high humiditycurl retention (HHCR). Descriptions of the HHCR methodology are readilyfound in the cosmetic literature. See, for example, Ch. 30, Harry'sCosmeticology, 8th Ed., M. J. Rieger, Ph.D. (ed.), 666-667, ChemicalPublishing Co., Inc., New York, N.Y. (2000), and Diaz et al., J. Soc.Cosmet. Chem., 34, 205-212 (July 1983), the relevant disclosures of eachare incorporated herein by reference.

[0135] Tresses of commercially blended Caucasian untreated (virgin)human hair were prepared employing natural brown or black color Europeanhair supplied by International Hair Importers and Products Inc., NewYork. Each hair tress (about 3 grams weight) was about 7 inches (about18 cm) in length and was anchored with glue at the scalp (root) endportion. Prior to use, each hair tress was pre-cleaned by washing with adilute aqueous solution of sodium lauryl sulfate (10% SLS), followed bythorough rinsing with deionized water at ambient room temperature anddried with towel blotting. The initial extended length of the hair(L_(e)) was measured. About 0.8 grams of polymer-containing compositionto be evaluated was applied to the hair tress and distributed uniformlyfrom the scalp to end portion. The treated hair tress was then wrappedaround a hair curler having an outer diameter of about 3 cm, and driedon the curler overnight at an ambient room temperature of about 21-23°C. (about 71-73° F.). After drying, the curler was carefully removed,leaving the hair styled into a single curl, the initial length of thehair curl (L_(i)) was measured, and the curled hair tress was verticallyhung in a humidity chamber set at an ambient temperature of about 26-27°C. and ambient high humidity of about 90% RH.

[0136] The resistance to high humidity, based on percent curl retention(HHCR) was determined by measuring the length of the hair curl as thecurl relaxed after selected intervals (L_(t)) of exposure to humidity.The following equation was used to calculate percent curl retention,relative to the initial curl length (L_(i)) and length of the fullyextended hair, before curling (L_(e)).${\% \quad {Curl}\quad {Retention}} = {\frac{L_{e} - L_{t}}{L_{e} - L_{i}} \times 100}$

[0137] The change in curl length (droop, helix formation) wasperiodically measured and monitored over a period in the range of about4 to about 24 hours with a final reading being taken after about 24hours. A retention of about 70% or more curl (HHCR) for a minimum periodof about 0.75 hours at about 90% RH is a conventional benchmark for goodhigh humidity resistance, and an HHCR greater than 70% after a period ofat least about 3 hours is judged very good to excellent.

[0138] G. Subjective Properties Assessment. The tactile, aesthetic andmechanical properties of hair treated with polymer-containingcomposition, such as feel, flaking, ease of combing, curl memory, suchas bouncy/curl-up, and static flyaway were subjectively assessed. Feelwas assessed by the psychosensory tactile characteristics of thepolymer-containing product (tackiness, smoothness, and the like) whilebeing hand applied to hair. Flaking of polymer on the hair, if any, wasassessed by inspecting the hair for visible deposit (coating) on thehair surface and by combing the treated hair and then inspecting thetines of the comb for visible residue. Combing ease and static flyawayof the hair was subjectively assessed during combing by noting hairtangles, flyaway fibers and difficulty in combing through the hair. Curlmemory was subjectively assessed by observing the bouncy, curl-upappearance of the hair curl pattern (i.e., complete curl, open helix orspiraling or loss of curl) remaining in the hair after exposure to highhumidity of about 90% RH.

[0139] H. Methods of Preparing Associative Polymers. A general emulsionpolymerization procedure preparation of alkali-swellable associativepolymers of the present invention is provided below:

[0140] A monomer emulsion is prepared in a first reactor equipped with anitrogen inlet and an agitator, by combining a desired amount of eachmonomer in water containing an emulsifying amount of an anionicsurfactant under a nitrogen atmosphere, with mixing agitation. To asecond reactor equipped with a mixing agitator, nitrogen inlet and feedpumps, are added a desired amount of water and additional anionicsurfactant, if desired, and the contents are heated under a nitrogenatmosphere with mixing agitation. After the second reactor reaches atemperature in the range of about 80-90° C., a desired amount of a freeradical initiator is injected into the surfactant solution in the secondreactor, and the monomer emulsion from the first reactor is thengradually pumped into the second reactor over a period in the range ofabout one to about four hours at a controlled reaction temperature inthe range of about 80-90° C. After completion of the monomer addition,an additional quantity of free radical initiator can be added to thesecond reactor, if desired, and the resulting reaction mixture is heldat a temperature of about 90-95° C. for a time period sufficient tocomplete the polymerization reaction, typically about 90 minutes. Theresulting polymer emulsion can then be cooled and discharged from thereactor.

[0141] I. Methods for Preparing Polymer-Containing Compositions. Forillustration, and not by limitation, product ASAP emulsions preparedaccording to the general Method H above were employed for preparing thecompositions in the following examples. Unless otherwise indicated, theproduct ASAP emulsions were diluted with water to obtain the desiredpolymer concentration or were added to a formulation with the watersoluble ingredients in an amount sufficient to provide the desiredpolymer concentration in the finished formulation. All references toweight % polymer means active weight % polymer on a total formulationweight basis. Unless otherwise indicated, formulations are preparedemploying conventional formulation techniques well known to thoseskilled in the formulation arts. The inventive polymers were suitablefor use as rheology modifiers, film-formers, thickeners, suspendingagents and the like as illustrated in the following examples.

EXAMPLE 1 Polymers

[0142] The alkali-swellable associative polymer, identified as Polymer Ain Table 2A, was prepared according to the general procedure describedas Method H, and as described in detail below.

[0143] A monomer reaction mixture was prepared in a first reactor, undera nitrogen atmosphere, using an agitator mixer rotating at about 500rpm, by combining about 117 parts by weight of methacrylic acid, about172 parts by weight of ethyl acrylate, about 25.5 parts by weight ofBEM25, and about 3.2 parts by weight of LEM23 into about 92 parts byweight of deionized water containing about 10.6 parts by weight of 30%aqueous sodium lauryl sulfate. To a second reactor, equipped with amixing agitator, nitrogen inlet and feed pumps, were added about 570parts by weight of deionized water and about 3.2 parts by weight of 30%aqueous sodium lauryl sulfate. The contents of the second reactor wereheated with mixing agitation at a rotation speed of about 200 rpm undera nitrogen atmosphere. After the contents of the second reactor reacheda temperature in the range of about 85-88° C., about 6.3 parts of 3.5%ammonium persulfate solution (a free radical initiator) was injectedinto the so-formed hot surfactant solution in the second reactor. Theaqueous emulsion of the monomer mixture from the first reactor wasgradually pumped into the second reactor over a period of about 60minutes at a controlled reaction temperature in the range of about85-88° C. At the completion of the monomer mixture addition, about 9.4parts by weight of 0.7% ammonium persulfate solution was added to thereaction mixture in the second reactor and the temperature of thereaction was maintained at about 90° C. for an additional one and halfhours to complete polymerization. The resulting ASAP emulsion was cooledto room temperature, discharged from the reactor and collected.

[0144] Comparative HASE Polymers, CP-1 through CP-6, each having themonomer components shown in Table 1, the inventive alkali-swellableASAP, Polymers B-M, N-Z and AA-AW, and alkali-soluble ASAP, PolymersBA-BL, each having the monomer components shown, respectively, in Tables2A, 2B, 2C, and 2D, respectively, were prepared following the generalmethod for the preparation of Polymer A, above. All monomers listed fora given polymer, were included in the monomer reaction mixture in thefirst reactor and the amounts of the monomers were adjusted, as needed,to achieve the monomer weight percent values listed in Tables 1, 2A, 2B,and 2C; all % values in the tables are weight percent, based on totalmonomer mixture weight.

[0145] All of the polymers were prepared as aqueous solutions havingtotal solids levels in the range of about 30 to about 45%. In mostcases, sodium lauryl sulfate (SLS) was utilized as the emulsifyingsurfactant for the polymerization reaction. In addition, Polymer AV wasalso successfully prepared according to the foregoing procedureutilizing a combination of SLS and nonionic emulsifying surfactant,i.e., Ceteareth-20 (INCI name for polyoxyethylene (20) cetyl/stearylether). In the preparations of Polymers BH, BK, and BL, the followingsurfactants were utilized in place of SLS, respectively: RHODAFAC® 610(a complex phosphate ester of a branched alcohol ethoxylate, availablefrom Rhodia, Inc., Cranbury, N.J.), disodium laureth-3-sulfosuccinate,and sodium dioctyl sulfosuccinate. TABLE 1 Comparative HASE PolymerCompositions Acidic Vinyl Nonionic Vinyl Associative Polymer No. Monomer(%) Monomer (%) Monomer(s) (%) Other Monomer(s) (%) CP-1 MAA (37) EA(53.7) BEM25 (9) EOBDMA (0.3) CP-2 MAA (37) EA (53) BEM25 (10) CP-3 MAA(37) EA (59.7) BEM25 (3) TMPTA (0.3) CP-4 MAA (37) EA (53.55) BEM25 (8);EOBDMA (0.3); CSEM25 (1) IMP (0.15) CP-5 MAA (36) EA (60.9) BEM25 (3)TMPTA (0.1) CP-6 MAA (37) EA (53.7) BEM25 (9) Diallyl phthalate (0.3)

[0146] TABLE 2A Inventive Polymer Compositions Nonionic Acidic VinylVinyl Associative Optional Monomer(s) Monomer(s) Monomers Monomer(s)Poly. No. (%) (%) (%) (%) A MAA (37) EA (54) BEM25 (8); LEM23 (1) B MAA(34); EA (55.85); BEM25 (4); TMPTA (0.1); AA (2) WAM (3) LEM23 (1)EOBDMA (0.05) C MAA (37) EA (53.7) BEM25 (8); EOBDMA (0.3) LEM23 (1) DMAA (37) EA (53.7) BEM25 (8); EOBDMA (0.3) HCOEM25 (1) E MAA (37) EA(53.7) BEM25 (8); EOBDMA (0.3) HCOEM16 (1) F MAA (37) EA (53.7) BEM25(8); EOBDMA (0.3) TEM25 (1) G MAA (37) EA (53.85) BEM25 (8); IMP (0.15)LEM23 (1) H MAA (37) EA (53.55) BEM25 (8); EOBDMA (0.3); LEM23 (1) IMP(0.15) I MAA (37) EA (53.85) BEM25 (8); ODM (0.15) LEM23 (1) J MAA (37)EA (53.55) BEM25 (8); ODM (0.15) LEM23 (1) EOBDMA (0.3) K MAA (37) EA(57.9) BEM25 (4); TMPTA (0.1) LEM23 (1) L MAA (37) EA (53.7) BEM25 (6);EOBDMA (0.3) LEM23 (3) M MAA (37) EA (57.7) BEM25 (4); TMPTA (0.15);LEM23 (1) EOBDMA (0.15)

[0147] TABLE 2B Inventive Polymer Compositions Nonionic Associative SHOptional Poly. Acidic Vinyl Vinyl Monomer(s) Monomer(s) Monomer(s) No.Monomer (%) Monomer (%) (%) (%) (%) N MAA (37) EA (59.7) CHEM24 (1.5);EOBDMA (0.3) CEM24 (1.5) O MAA (37) EA (56.7) BEM25 (3); EOBDMA (0.3)CHEM24 (1.5); CEM24 (1.5) P MAA (37) EA (59.9) BEM25 (2); TMPTA (0.1)LEM23 (1) Q MAA (36) EA (58.1) BEM25 (2); R307 (2.8) TMPTA (0.1) LEM23(1) R MAA (35) EA (58.9) BEM25 (2); M5010 (3) TMPTA (0.1) LEM23 (1) SMAA (35) EA (56.9) BEM25 (2); R307 (3); TMPTA (0.1) LEM23 (1) M5010 (2)T MAA (37) EA (42.8) BEM25 (15); TMPTA (0.05); LEM23 (5) EOBDMA (0.15) UMAA (37) EA (57.8) BEM25 (4); TMPTA (0.2) LEM23 (1) V MAA(37) EA (53.7)BEM25 (3); EOBDMA (0.3) LEM23 (6) W MAA (37) EA (53.7) BEM25 (4.5);EOBDMA (0.3) LEM23 (4.5) X MAA (36) EA (55.9) BEM25 (2); BX-AA (5) TMPTA(0.1) LEM23 (1) Y MAA (36) EA (54.9) BEM25 (3); R307 (5) TMPTA (0.1)LEM23 (1) Z MAA (36) EA (55.9) BEM25 (2); R307 (5) TMPTA (0.1) LEM23 (1)

[0148] TABLE 2C Inventive Polymer Compositions Nonionic Acidic VinylVinyl Associative Optional Poly. Monomer(s) Monomer(s) Monomer(s) SHMonomer No. (%) (%) (%) Monomer (%) (%) AA MAA (37); EA (51) BEM25 (6);SSSA (5) LEM23 (1) AB MAA (36) EA (55.2) BEM25 (2.5); R307 (5) EOBDMA(0.3) CHEM24 (0.5); CEM24 (0.5) AC MAA (52); EA (42.7) BEM25 (2); EOBDMA(0.3) AA (2) LEM23 (1) AD MAA (36) EA (48.7) BEM25 (10); EOBDMA (0.3)LEM23 (5) AE MAA (37) EA (59.7) BEM25 (2); EOBDMA (0.3) LEM23 (1) AF MAA(36) EA (58.4) BEM25 (3) R307 (2.5) TMPTA (0.1) AG MAA (36) EA (55.9)BEM25 (3) R307 (5) TMPTA (0.1) AH MAA (36) EA (53.4) BEM25 (3) R307(7.5) TMPTA (0.1) AI MAA (36) EA (45.9) BEM25 (3) R307 (15) TMPTA (0.1)AJ MAA (37) EA (53.7) BEM25 (8) MPEG35 (1) EOBDMA (0.3) AK MAA (37) EA(53.7) BEM25 (8) MPEG55 (1) EOBDMA (0.3) AL MAA (2.5); EA (57.5) BEM25(8) MPEG55 (1) AA (31) AM MAA (36) EA (57.9) BEM25 (2); R307 (3) TMPTA(0.1) CHEM24 (0.5); CEM24 (0.5) AN MAA (35) EA (56.9) BEM25 (4); M5010(3) TMPTA (0.1) LEM23 (1) AO MAA (36) EA (52.9) BEM25 (4); BX-AA (3)TMPTA (0.1) WAM (3) LEM23 (1) AP MAA (36) EA (50.9) BEM25 (4); BX-AA (5)TMPTA (0.1) WAM (3) LEM23 (1) AQ MAA (36) EA (53.85) BEM25 (4); BX-AA(5) TMPTA (0.15) LEM23 (1) AR MAA (37) EA (48.8) CSEM25 (9) BX-AA (5)TMPTA (0.2) AS MAA (36) EA (54.7) BEM25 (8); TMPTA (0.3) LEM23 (1) ATMAA (37) EA (51.8) CSEM25 (10) BX-AA (1) TMPTA (0.2) AU MAA (37) EA(51.8) CSEM25 (10) R307 (1) TMPTA (0.2) AV MAA (37) EA (52.8) CSEM25 (8)BX-AA (2) TMPTA (0.2) AW MAA (47) EA (46.8) CSEM25 (4) BX-AA (2) TMPTA(0.2)

[0149] TABLE 2D Inventive Polymer Compositions Nonionic Chain AcidicVinyl Vinyl Associative Transfer Poly. Monomer(s) Monomer(s) Monomer(s)SH Monomer Agent No. (%) (%) (%) (%) (%) BA MAA (29); EA (43.2); BEM25(2.5); R307 (2); DDM (0.8) MMA (19.5) LEM23 (1) M5010 (2) BB MAA (28.64)EA (44.44); BEM25 (2.47) R307 (1.975); DDM (1.24) MMA (19.26) M5010(1.975) BC MAA (28.64) EA (44.44); LEM25 (2.47) R307 (1.975); DDM (1.24)MMA (19.26) M5010 (1.975) BD MAA (28.64) EA (44.44); CSEM25 (2.47) R307(1.975); DDM (1.24) MMA (19.26) M5010 (1.975) BE MAA (25) EA (47.74)BEM25 (2.5) R307 (2); DDM (1.26) MMA (19.5) M5010 (2) BF MAA (29) EA(43.74) LEM25 (2.5) R307 (2); DDM (1.26) MMA (19.5) M5010 (2) BG MAA(29) EA (43.74) CSEM25 (2.5) R307 (2); DDM (1.26) MMA (19.5) M5010 (2)BH MAA (24.78) EA (48.56) BEM25 (2.48) R307 (1.98); DDM (0.89) MMA(19.33) M5010 (1.98) BI MAA (25) EA (50.74) BEM25 (2.5) M5010 (1) DDM(1.26) MMA (19.5) BJ MAA (25) EA (50.74) BEM25 (2.5) BX-AA (1) DDM(1.26) MMA (19.5) BK MAA (17.5) EA (52.74) BEM25 (2.5) BX-AA (1) DDM(1.26) MMA (25) BL MAA (25) EA (50.74) CSEM25 (2.5) BX-AA (1) DDM (1.26)MMA (19.5)

[0150] After the preparation of the polymers, product emulsions areanalyzed to determine the pH, percent total solids (TS) based on polymercontent, and Brookfield viscosity (spindle #2, 20 rpm, ambient roomtemperature). Additionally, the glass transition temperature (Tg) ofselected product polymers are determined by Method C above. The productpolymer emulsions, as produced, generally have a pH of not more thanabout 5.5, typically in the range of about pH 2.5-4.5; total solids (TS)in the range of about 15 to about 45 weight percent; a Brookfieldviscosity in the range of about 10 to not more than about 100 mPa·s, anda Tg in the range of about 35° C. to about 150° C. The pH of the polymeremulsions can be adjusted with acidic agents or alkaline agents to a pHpreferably in the range of about 3 to 7.5, or until the composition issubstantially clear or translucent, as desired. Where clarity is not aproblem or where alkaline pH is desired, the pH of the composition canbe adjusted to an alkaline pH of even greater than 12 and remain alkalistable as illustrated in the following examples.

EXAMPLES 2-8 Aqueous Gels

[0151] The aqueous gels were prepared by diluting the product polymeremulsion with water to obtain the desired active polymer concentrationand then neutralizing the diluted polymer emulsion with2-amino-2-methyl-1-propanol (AMP, 95%) to a pH of about 5.8 to about7.5, or until the composition was substantially clear. The % clarityvalue was obtained by Method B, the viscosity was measured by Method A.The results obtained are set forth in Table 3.

[0152] These examples illustrate the rheology modification and clarityachieved in aqueous gels containing the inventive polymers. ComparativeExamples 2 and 3, illustrate the viscosity, and clarity of aqueous gelscontaining Comparative Polymer CP-1 of Example 1, a crosslinked,hydrophobically modified alkali-swellable emulsion (HASE) polymer havingone associative monomer, in the amounts shown in Table 3. Examples 4 to8 illustrate the thickening and clarity of aqueous gels containing,respectively, one the following inventive crosslinked ASAP from Example1, Polymer C, D, E, or F, in the amount indicated in Table 3, eachemploying one associative monomer (BEM25) that is the same associativemonomer of Comparative Polymer CP-1, and various different associativemonomers (i.e., a linear alkyl group (LEM23), complex ester (HCOEM25),or aryl-substituted alkyl group (TEM25)). TABLE 3 Viscosity ViscosityEx. Poly. Wt % mPa · s mPa · s No. No. Poly. pH % Clarity Immed. 24 hrs.2 CP-1 1 7.4 67.5 14,300 18,400 3 CP-1 1.2 7.3 67.1 21,750 36,800 4 C 16.6 68.0 14,100 30,600 5 C 1.2 6.6 68.3 28,900 51,400 6 D 1.2 6.5 81.528,600 32,980 7 E 1.2 6.8 65.1 32,200 57,400 8 F 1.2 6.5 69.5 29,20056,400

[0153] As shown in Table 3 each of the aqueous compositions containingthe inventive Polymers, C-F, achieved an initial gel viscositysubstantially similar to or greater than that of Comparative HASEPolymer CP-1 at corresponding active polymer concentration of about 1and about 1.2 weight %. After 24 hours, the viscosity of all the gels ofPolymers C-F was substantially greater than the gels of Comparative HASEPolymer CP-1 at the corresponding concentration. Further, the aqueousgels made with the inventive Polymers C-F achieved clarity at a lower pH(pH <7) than did Comparative Polymer CP-1 (pH >7).

[0154] For further comparison, the gels of examples 2 and 3 wererepeated, except that the Comparative HASE Polymer, CP-6, was employed.At an active CP-6 polymer weight of about 1% and about pH 7.4, the24-hour viscosity was 6,500 mPa·s and the % clarity was only about 26.2.At an active CP-6 polymer weight of about 1.2% and about pH 6.7, the24-hour viscosity was about 17,300 mPa·s and the % clarity was onlyabout 29.9.

EXAMPLES 9-11 Aqueous Gels

[0155] Examples 9-11 respectively illustrate the viscosity and clarityachieved in aqueous gels containing the inventive Polymers A, K and L ofExample 1, each at active polymer concentrations of about 1.2 weight %,as shown in Table 4 below. Polymer A is a non-crosslinked analog ofPolymer C of Example 5. Polymers K and L illustrate crosslinked polymershaving different crosslinkers and varying hydrophobe content. The gelswere prepared and neutralized to the pH indicated, and viscosity and %clarity determined as described in Examples 2-8. TABLE 4 ViscosityViscosity Ex. Poly. Wt % mPa · s mPa · s No. No. Poly. pH % ClarityImmed. 24 hrs 9 A 1.2 6.8 79.9 49,980 116,200 10 K 1.2 6.6 77.7 30,50062,600 11 L 1.2 7.2 80.1 39,800 86,800

[0156] As shown in Table 4, the gel made with the inventivenon-crosslinked Polymer A (Ex. No. 9) had better clarity and higherviscosity than the gel containing non-crosslinked Polymer C of Example5. The aqueous gels made with Polymers K and L (Ex. Nos. 10 and 11) alsodemonstrate good thickening and clarity.

EXAMPLES 12-13 Aqueous Gels

[0157] Examples 12-13 illustrate the viscosity and clarity achieved inaqueous gels containing the inventive ASAP of Example 1, Polymer N (Ex.12A, 12B) and Polymer O (Ex. 13A, 13B), at the various active weight %indicated in Table 5. Polymer O has three different associativemonomers, two of which have linear alkyl hydrophobic end groups, and oneof which has a carbocyclic alkyl hydrophobic end group; whereas PolymerN has two associative monomers, one having a linear alkyl hydrophobicend group, and the other a carbocyclic alkyl hydrophobic end group. Theaqueous gels were prepared and neutralized to the pH indicated, andviscosity and % clarity determined as described in Examples 2-8. TABLE 5Viscosity Viscosity Ex. Poly. Wt % % mPa · s mPa · s No. No. Polymer pHClarity Immed. 24 hrs. 12A N 1.5 6.5 79.9 23,450 32,400 12B N 2 6.3 79.234,350 51,600 13A O 1.5 6.6 54 66,800 85,800 13B O 2 6.5 52.2 122,800164,800

[0158] Table 5 shows that, at the same active polymer concentration, theinventive Polymer O provided gels with greater viscosities than PolymerN.

EXAMPLES 14-15 Aqueous Gels

[0159] Examples 14-15 illustrate the viscosity and % clarity in aqueoushair setting compositions containing 1.2 or 1.5 active weight % of ASAP,Polymer AB (Ex. 14A, 14B) or Polymer AM (Ex. 15A, 15B) of Example 1.Polymers AB and AM each have three different associative monomers, twoof which have linear alkyl hydrophobic end groups and one of which has acarbocyclic alkyl hydrophobic end group. The polymers have the same typeof semihydrophobic monomers and different types of crosslinkingmonomers.

[0160] The compositions were prepared employing the formulation shown inTable 6. TABLE 6 Ingredient Wt % Polymer, as indicated below 1-1.5Propylene glycol 0.5 Metal ion Chelating Agent 0.1 Preservative 0.5 AMPto pH indicated below q.s. Deionized Water to 100% q.s.

[0161] The viscosity was measured by Method A, and the % clarity wasobtained by Method B as shown below in Table 7. TABLE 7 Polymer ABPolymer AM Ex. 14A Ex. 14B Ex. 15A Ex. 15B Polymer % (active) 1.2 1.51.2 1.5 pH 6.5 6.5 6.7 6.7 % Clarity 77.2 76.3 83.8 81.2 Viscosity (mPa· s) Immediate 4,740 13,460 21,150 39,550 24 hour 7,400 16,650 30,80039,800

[0162] Polymer AM provided a greater viscosity than Polymer AB. Bothpolymers provided products having very good clarity.

EXAMPLES 16-28 Aqueous Gels

[0163] Examples 16-28 illustrate the clarity and viscosity achieved inaqueous gels containing the following ASAP of Example 1, crosslinkedPolymers E (Exs. 16 A, B), F (Exs. 17A, B), H (Exs. 19A-C), J (Exs. 21A,B), K (Exs. 22 A, B), L (Ex. 23A, B), M (Ex. 24 A-C) AT (Exs. 25 A-D),AU (Exs. 26 A-C), AV (Exs. 27A, B), AW (28 A, B) and non-crosslinkedPolymers G (Exs. 18 A-C) and I (Exs. 20 A, B) at various active weight %concentrations as indicated in Table 8 below. Crosslinked Polymers H andJ and non-crosslinked Polymers G and I contain chain transfer agents.Polymer M contains two crosslinking agents, one of which is ethoxylated.Polymers AT, AU, AV, and AW contain semihydrophobic monomer. The aqueousgels were prepared and neutralized to the pH indicated, and viscosityand % clarity determined as described in Examples 2-8. The results areshown in Table 8. TABLE 8 Viscosity Viscosity Ex. Poly. Wt % % mPa · smPa · s No. No. polymer pH Clarity Immed. 24 hr 16A E 1.5 6.8 65 73,200109,800 16B E 1.8 6.8 64.7 120,800 144,600 17A F 1.5 6.5 69.2 49,80094,800 17B F 1.8 6.4 68.7 73,400 117,600 18A G 1.5 6.4 92.1 27,55034,000 18B G 1.8 6.3 91.8 27,350 36,200 18C G 2 6.3 91 45,650 66,800 19AH 1.5 6.3 95.9 30,950 37,200 19B H 1.8 6.3 94.2 46,450 57,800 19C H 26.4 94 79,800 86,600 20A I 1 6.4 96.5 23,800 35,050 20B I 1.2 6.2 9542,600 79,200 21A J 1 6.2 94.6 19,600 25,850 21B J 1.2 6.1 97 35,90068,200 22A K 1.5 6.6 75.2 65,200 96,200 22B K 1.8 6.6 70.3 103,200136,200 23A L 1.5 7 83.3 58,200 97,200 23B L 1.8 7.1 79.9 136,600164,800 24A M 1.5 6.6 60.3 39,600 56,200 24B M 1.8 6.6 55.9 49,40084,600 24C M 2 6.7 48.7 93,600 119,400 25A AT 1 6.5 86.2 9,700 11,20025B AT 1.2 6.5 84.3 13,850 14,000 25C AT 1.5 6.5 82.5 36,200 44,400 25DAT 2 6.5 85.8 71,600 78,200 26A AU 1 6.3 89.1 6,720 7,850 26B AU 1.2 6.387.2 8,100 9,300 26C AU 1.5 6.2 86.6 12,400 13,050 27A AV 1.5 6.5 92.3 —23,200 27B AV 2 6.5 93.6 — 50,000 28A AW 1.5 6.5 86.2 — 18,500 28B AW 26.5 87.6 — 32,700

[0164] The viscosities of all the aqueous gels containing Polymers E-M(Exs. 16-24) underwent a substantial increase as these aqueouscompositions aged over 24 hours or so. Polymers G, H, I, J and Kdemonstrated a surprisingly enhanced clarity and viscosity, greater thaneven that of Polymers E, F, L and M at similar concentration.

[0165] Surprisingly, the viscosity of Polymers AT-AU was substantiallyunchanged over 24 hours or so. Polymers AT-AW were judged suitable foreither high viscosity or gel compositions.

EXAMPLE 29 Aqueous Gels

[0166] This example demonstrates that ASAP can be combined withhydrophobically-modified carbomer polymer to provide gels (i.e., havinga Brookfield viscosity above 10,000 mPa·s) over a broad pH range ofabout 5.3 to about 13.3.

[0167] Nine aqueous gels (Exs. 29A-I) were separately prepared, eachcontaining, on a final weight basis, about 0.8 active weight % ASAP,Polymer AT of Ex. 1, and about 0.4 active weight %hydrophobically-modified carbomer polymer, CARBOPOL® Ultrez 21 polymer,(Noveon, Inc., Cleveland, Ohio), and each gel respectively havingsufficient neutralizing base (sodium hydroxide, 18%) to obtain a pH of5.3 (Ex. 29A), 7 (Ex. 29B), 8 (Ex. 29C), 9.1 (Ex. 29D), 10 (Ex. 29E),11.5 (Ex. 29F), 12.3 (Ex. 29G), 13.1 (Ex. 29H), and 13.3 (Ex. 291). Theviscosity of each gel was determined as described in Method A.Surprisingly, as shown by the following results, gels were obtained atall pH values: Brookfield viscosity in mPa·s was 49,800 (Ex. 29A);86,400 (Ex. 29B); 75,800 (Ex. 29C); 69,400 (Ex. 29D); 65,500 (Ex. 29E);63,700 (Ex. 29F); 57,600 (Ex. 29G); 32,100 (Ex. 29H); and 24,800 (Ex.291). Also demonstrated was that the two anionic polymers werecompatible over the entire pH range examined.

EXAMPLE 30 Aqueous Gels

[0168] Electrolytes are generally known to reduce the viscosity obtainedwith conventional carbomer polymer thickeners. This example demonstratesthat generally unexpectedly high viscosity surprisingly can be achievedwith ASAP, Polymer AT of Example 1, in the presence of an electrolyte(e.g., sodium chloride), in combination with a hydrophobically modifiedcarbomer polymer, CARBOPOL® Ultrez 21 polymer, (Noveon, Inc., Cleveland,Ohio).

[0169] Gel Series A. An aqueous gel was prepared containing, on a totalweight basis, about 1.25 weight % Polymer AT of Example 1, neutralizedwith AMP to about pH 6.4-6.8. The gel had a Brookfield viscosity ofabout 22,400 mPa·s. The procedure was repeated to provide three separateaqueous gels, except that each gel also contained, respectively, thefollowing weight % of sodium chloride, 0.1, 0.25, and 0.5. The saltdecreased the Brookfield viscosity of the ASAP gel to about 8,100 mPa·s(0.1% salt), to about 3,200 mPa·s (0.25% salt) and to about 900 mPa·s(0.5% salt).

[0170] Gel Series B. The procedure of Series A was repeated, except thatthe aqueous gels contained, on a total weight basis, about 1.25 activeweight % CARBOPOL® Ultrez 21 polymer. The Brookfield viscosity of thesalt free gel was about 98,200 mPa·s, which was decreased by the salt toabout 61,800 mPa·s (0.1% salt), to about 44,600 mPa·s (0.25% salt), andto about 28,400 mPa·s (0.5% salt).

[0171] Gel Series C. The procedure of Series A was repeated, except thatthe aqueous gels contained, on a total weight basis, a total polymerweight of about 1.25 weight % comprised of about 0.75 active weight %Polymer AT and about 0.5 active weight % CARBOPOL® Ultrez 21 polymer.The Brookfield viscosity of the salt free gel was about 105,000 mPa·s.The Brookfield viscosity in the presence of salt remained unexpectedlyhigh at about 71,200 mPa·s (0.1% salt), about 55,800 mPa·s (0.25% salt),and about 42,050 mPa·s (0.5% salt).

[0172] The data surprisingly show that a combination of the ASAP andhydrophobically modified carbomer polymer provided gels having agenerally unexpectedly higher viscosity in the presence of electrolyte,as well as a generally higher salt tolerance than that of gelscontaining the individual polymer.

EXAMPLE 31 Sunscreen Lotions and Creams

[0173] This example illustrates the compatible use, on a totalcomposition weight basis, of a combination of ASAP, Polymer AT ofExample 1, at either about 0.5 active weight % (Ex. 31A) or about 1active weight % (Ex. 31B) with about 0.15 active weight % carbomerpolymer, CARBOPOL® 980 polymer, (Noveon, Inc., Cleveland, Ohio), in awater-resistant type sunscreen formulation having a high SPF (SunProtective Factor) value of greater than about 30.

[0174] In addition to the foregoing polymers, the sunscreen formulationsof Ex. 31A and 31B each also contained, on a total composition weightbasis, about 2 active weight % hexylene glycol, about 7.5 active weight% octyl methoxycinnamate, about 6 active weight % benzophenone-3, about5 active weight % octyl salicylate, about 10 active weight %octylcrylene, about 2 active weight % PEG-20 stearate (INCI name forCERASYNT 840, ISP Van Dyk & Co., Belleville N.J.), about 5 weight %glyceryl stearate(and)laureth-23 (INCI name for CERASYNT 945, ISP VanDyk & Co., Belleville N.J.), preservative (q.s.), deionized water (q.s.to 100 weight %) and sufficient base (triethanolamine, 99%) to obtain apH in the range of about 6.5-6.6.

[0175] The Brookfield viscosity for Ex. 31A was about 19,400 mPa·s andfor Ex. 31B was about 40,800 mPa·s. The viscosity remained substantiallyunchanged over a storage period of about two months at a temperature ofabout 45° C. The sunscreen of Ex. 31 A was an aesthetically smooth,glossy lotion and that of Ex. 31B was an aesthetically smooth, glossycream. Both sunscreens were judged as having excellent spreadability,and rich, firm, textural, sensory product attributes.

EXAMPLES 32-35 Skin Care Lotion

[0176] Examples 32-35 illustrate the stabilization of a skin care lotionformulation containing, on a total composition basis, about 0.25 activeweight % of the humectant salt, sodium PCA (INCI name for the sodiumsalt of DL-pyrrolidone carboxylic acid, sold under the trade nameAJIDEW® N-50, by Ajinomoto Inc., Teaneck, N.J.), employing relativelylow concentrations of ASAP, Polymer AT of Example 1, alone or incombination with hydrophobically-modified carbomer polymer, CARBOPOL®Ultrez 21 polymer, (Noveon, Inc., Cleveland, Ohio), while achieving highviscosity.

[0177] Five skin care lotions were separately prepared containing as thestabilizer, the following amounts, on a total composition weight basis:about 0.6 active weight % Polymer AT (Ex. 32A), about 1 active weight %Polymer AT (Ex. 32B); about 0.3 active weight % Polymer AT and about 0.3active weight % CARBOPOL® Ultrez 21 polymer (Ex. 33); about 0.6 weight %Polymer AT and about 0.3 active weight % CARBOPOL® Ultrez 21 polymer(Ex. 34); and about 0.6 active weight % of the carbomer polymer (Ex.35).

[0178] Each of the skin care lotions contained, in addition to theforegoing sodium PCA and polymer indicated, on a total compositionweight basis, about 2 active weight % glycerin, about 3 active weight %sunflower seed oil, about 5 active weight % caprylic/caprictriglycerides, about 4 active weight % cetearyl octanoate, about 3active weight % cocoa butter, preservative (q.s.), fragrance (q.s.), andsufficient AMP (95%) to obtain about pH 6.4-6.5.

[0179] The lotions of Exs. 32A, 32B, and 35 were prepared by generallyrecognized emulsion technique by combining the water insolublecomponents together to provide an oil phase, combining the glycerin,water, and polymer to provide a water phase, adding the oil phase to thewater phase, then adding the preservative and fragrance, and adjustingthe pH, as needed. The lotions of Exs. 33 and 34 were similarlyprepared, except that the polymers were blended by pre-dispersing theCARBOPOL® Ultrez 21 polymer in a portion of the water, then adding thePolymer AT was added to the dispersion, neutralizing the resultingpolymer blend, and then incorporating the resulting polymer blend intothe water phase.

[0180] All of the skin care lotions containing ASAP (Exs. 32A, 32B, 33and 34) produced products having a Brookfield viscosity greater than10,000 mPa·s and remained physically stable, even after storage for aperiod of at least two months at ambient room temperature and atelevated temperature (45° C.), with no loss in viscosity. In contrast,the lotion of Ex. 35 containing no ASAP was not stabilized (separatedinto two phases substantially immediately). All of the stabilizedlotions of Exs. 32-34 were judged aesthetically smooth, and easy tospread. The sensory tactile properties of the lotion of Ex. 34 werefurther enhanced by repeating the preparation of the lotion and furtherincluding about 0.6 active weight % of dimethicone PEG-7 isostearate(INCI name for a water-dispersible dimethicone copolyol ester sold underthe trade name, ULTRASIL™ DW-18 silicone, by Noveon, Inc., ClevelandOhio) without loss in stability, or viscosity under the foregoingstorage temperatures and periods.

EXAMPLE 36 Alkali-Soluble Associative Polymers

[0181] Alkali-soluble ASAP of the present invention, exemplified byPolymers BA through BL of Ex. 1, Table 2D, are judged useful in avariety of applications as foam enhancers, and as film formers inproducts where relatively low thin viscosity is desired.

[0182] Aqueous solutions of Polymers BE, BF, BG, BI, BJ and BK, each ofwhich contains one associative monomer, were prepared at active polymerweight concentrations of about 3, 5, and 10%, and were neutralized to apH in the range of about 6.5 to about 7.5 with AMP (95%). At a polymerconcentration of about 3% by weight, the Brookfield viscosities of thesolutions were too low to measure. At about 5% by weight, each of thepolymers afforded a solution having a Brookfield viscosity of not morethan about 25 mPa·s. Even at about 10% concentration, the polymers allafforded aqueous solutions with Brookfield viscosities of not more thanabout 300 mPa·s.

[0183] The foregoing procedure was repeated, except that the aqueoussolutions contained Polymer BA, which has two associative monomers. TheBrookfield viscosity, at a Polymer BA concentration of about 3% was lessthan about 15 mPa·s, of about 5%, was about 61 mPa·s, and of about 10%was about 850 mPa·s.

[0184] In contrast, a 5% solution of a polymer similar to Polymers BIand BJ, but lacking the semihydrophobic monomer (i.e., a polymercomprising 48.2% EA, 19.5% MMA, 29% MAA, 2.5% BEM25, and 0.8% DDM) had aBrookfield viscosity of greater than about 3,000 mPa·s and anundesirable stringy texture. Similarly, a 5% solution of another similarpolymer having neither a semihydrophobic monomer nor a chain transferagent (i.e., a polymer comprising 49% EA, 19.5% MMA, 29% MAA and 2.5%BEM25) had a Brookfield viscosity of greater than about 300,000 mPa·sand an undesirable lumpy texture.

[0185] The alkali-soluble associative polymers of the present inventionare judged as excellent foam enhancers for aqueous and hydro-alcoholicpump and spray foam products, such as shaving creams, foaming hairfixatives, foam-type cleansing agents, and the like. The polymers arecompatible and soluble in aqueous alcohol solutions containing up to atleast about 55% by volume ethanol, at polymer concentrations of at leastabout 5% by weight making them suitable for low VOC (not more than about55% volatile organic compounds) compositions.

[0186] The alkali-soluble associative polymers of the present inventionare also compatible with hydrocarbons, making the polymers useful inhigh VOC pressurized or non-pressurized aerosol spray applications (upto at least about 85% VOC) as well. For example, in a solution of about20% by volume cyclohexane in ethanol (95%) the solubility of Polymer BJof Ex. 1 was about 5 active weight % at room temperature and about 2active weight % at a temperature of about 4° C. In a solution of 50% byvolume cyclohexane in ethanol (95%), Polymer BJ was soluble at aconcentration of about 1 active weight % at both room temperature and atabout 4° C. The solutions remained clear and transparent (i.e., nocloudiness was observed).

[0187] Polymers BG and BI were each separately formulated in 55% aqueousethanol at a level of about 5 active weight % polymer and neutralizedwith AMP (95%) to a pH in the range of about 7 to about 8. Each ASAPprovided a solution having a Brookfield viscosity of about 5 mPa·s.Polymer BG provided a fine mist spray when pumped from a manuallyactuated pump sprayer. Polymer BI afforded a rich, thick, glossy foamwhen dispensed from a mechanical, non-pressurized aerosol foam dispenser(e.g., mechanical foam dispensers available from Airspray International,Inc., Pompano Beach, Fla.). Both formulations provided excellent highhumidity resistance, based on Method F when applied to hair, did notleave a flaky residue on the hair and washed out easily.

[0188] The alkali-soluble ASAP are judged suitable for use inhydrocarbon-based (e.g., n-butane, pentane, and isobutane) pressurizedaerosol formulations and for non-pressurized aerosol formulations whereno chemical or gaseous propellants are used.

EXAMPLE 37 Humidity Resistance

[0189] The humidity resistance of the hair tresses treated by theinventive polymers was assessed by the procedure of Method F, based onan HHCR of a minimum of 70% Curl Retention on hair. The aqueous gelcompositions containing Polymers C, D, E and F of Examples 4-8 and16-19, Polymers A, K and L of Examples 9-11, Polymers N and O ofExamples 12-13, Polymers G-M and AT-AW of Examples 18-28 were evaluated.Surprisingly, all of the inventive polymers demonstrated very good toexcellent high humidity resistance, i.e., an HHCR of at least 70% ormore curl retention for a minimum of about four hours. The subjectivecurl memory (bouncy/restylability) properties of the curled hairassessed by Method G above were also judged good to excellent afterexposure to 90% RH over 24 hours indicating that the inventiveassociative polymers were suitable for use in hair care applications forhair setting and styling.

EXAMPLES 38-40 Aqueous Formulations

[0190] The procedure of Examples 14-15 was followed except that theinventive ASAP of Example 1, Polymers P (Ex 38A, 38B, 38C), Q (Ex. 39A,39B, 39C), and R (Ex. 40A, 40B, 40C) were employed in the amounts shownin Table 7. Each of Polymers P, Q, and R has the same type ofassociative monomer and crosslinker; and Polymers Q and R also containdifferent semihydrophobic monomers.

[0191] Additionally, the gel texture was assessed by spreading a portionof the gel or viscous formulation over a MYLAR® film substrate employinga 10 mil opening draw down applicator and observing its smoothness andspreadability characteristic. When the texture of the gel coating wassmooth and spreadable, it was rated as “S”; when the gel coatingappeared grainy, it was rated as “G”. The results are shown in Table 9below. TABLE 9 Visc. Visc. Ex. Poly. Wt % % mPa · s mPa · s Gel No. No.Poly. pH Clarity Immed. 24 hrs. Texture 38A P 1 6.8 88.2 13,500 14,800 S38B P 1.2 6.8 84.6 24,500 26,750 S 38C P 1.5 6.8 81.7 39,750 42,500 G39A Q 1 6.8 71.8 8,800 9,200 S 39B Q 1.2 6.8 63.6 13,750 13,500 S 39C Q1.5 6.9 65 26,250 27,000 S 40A R 1 6.9 94.9 9,500 10,000 S 40B R 1.2 6.992.8 19,500 19,500 S 40C R 1.5 6.8 93.8 27,250 29,000 S

[0192] As shown in Table 9, all the polymers produced “S” gel textures,except for the crosslinked Polymer P at a concentration of 1.5% (Ex.38C). The texture of the gels obtained with Polymers Q and R were judgedto be soft, smooth, and spreadable, even as the concentration of thepolymer increased, compared to the texture of the gels obtained withPolymer P, containing no semihydrophobic monomer. Additionally, PolymersQ and R produced gels having a viscosity that remained substantiallyunchanged over a 24-hour period.

[0193] Surprisingly, at all concentrations, Polymers P, Q and Rdemonstrated good to excellent high humidity resistance, based on anHHCR of greater than 70% curl retention by Method F over a period ofabout four hours exposure.

EXAMPLE 41-44 Aqueous Formulations

[0194] In Examples 41-44, the procedure of Examples 38-40 was followedexcept that the inventive ASAP of Example 1, Polymers AF (Ex. 41A, B),AG (Ex. 42A, B), AH (Ex. 43A, B), and AI (Ex. 44A, B), were employed atthe amounts shown in Table 10. The polymers have varying amounts of thesame type of semihydrophobic monomer.

[0195] The aqueous gels were prepared and neutralized to the pHindicated in Table 10 below as described in Examples 2-8. The texture ofthe gels was evaluated as described in Examples 38-40. The results arein Table 10. TABLE 10 Visc. Visc. Ex. Poly. Wt % % mPa · s mPa · s GelNo. No. Poly. pH Clarity Immed. 24 hrs. Texture 41A AF 1 7 83.6 18,60026,650 S 41B AF 1.2 6.9 82.9 23,650 34,900 S 42A AG 1 6.9 67 13,55018,350 S 42B AG 1.2 6.9 65.8 21,050 32,400 S 43A AH 1 7 85.5 16,70025,450 S 43B AH 1.2 6.9 86.4 22,950 36,400 S 44A AI 1 6.7 93.6 16,55023,500 S 44B AI 1.2 6.6 92.8 21,700 28,800 S

[0196] The data show that at all concentrations, the texture of the gelproduced was smooth and spreadable (“S”). Each of the polymer gels wasalso found to have excellent high humidity resistance, based on an HHCRof greater than 70% curl retention by Method F over a period of morethan four hours exposure. Surprisingly, varying the amount ofsemihydrophobic monomer from about 2.5 weight % (Polymer AF) up to about15 weight % (Polymer Al) had no adverse effect on the viscosity of thegels at each concentration.

EXAMPLES 45-50 Aqueous Gels

[0197] The procedure of Examples 14-15 was followed, except that theASAP of Example 1, Polymer X (Ex. 45A, 45B, 45C), Polymer Y (Ex. 46A,46B, 46C), Polymer Z (Ex. 47A, 47B, 47C), Polymer AO (Ex. 48A, 48B),Polymer AP (Ex. 49A, 49B), and Polymer AQ (Ex. 50A, 50B), were employedin the amounts shown in Table 11. Each polymer contains; asemihydrophobic monomer component and two associative monomercomponents; and Polymers AO and AP each also have two nonionic vinylmonomer components.

[0198] The % clarity and viscosity at various active weight % polymer asindicated are shown in Table 11. TABLE 11 Visc. Visc. Ex. Poly. Wt % %mPa · s mPa · s No. No. Poly. pH Clarity Immed. 24 hrs. 45A X 1 6.9 90.411,600 12,800 45B X 1.2 6.9 90.9 20,000 20,500 45C X 1.5 6.8 88.1 38,75038,250 46A Y 1 6.8 81.4 12,800 14,100 46B Y 1.2 6.9 83.3 24,750 28,50046C Y 1.5 6.8 86.3 59,000 63,000 47A Z 1 6.8 79 7,700 7,760 47B Z 1.26.9 78.5 15,500 14,960 47C Z 1.5 6.8 78 27,500 31,350 48A AO 1 6.4 80.28,230 11,650 48B AO 1.5 6.8 81.7 22,790 37,850 49A AP 1 6.9 89.2 9,78014,890 49B AP 1.5 6.9 88.7 20,960 38,970 50A AQ 1 7 78.1 9,440 13,99050B AQ 1.5 7.2 78 27,940 47,700

[0199] The data show that each of the Polymers demonstrated good clarityand viscosity. The high humidity resistance of each of the polymers wasalso judged excellent, based on 70% curl retention for more than fourhours exposure.

EXAMPLE 51 Aqueous Silicone Gels

[0200] This example illustrates aqueous silicone-containing gelsprepared employing ASAP of Example 1, Polymer K (Ex. 51A) and Polymer M(Ex. 51B), in the amounts and composition shown in Table 12. TABLE 12Ex. 51A Ex. 51B Ingredients Weight % Weight % Polymer 1 1.5 AMP (95%) TopH 7.4 To pH 6.4 Dimethicone PEG-7 1.5 1 phthalate (Note 1) Preservativeq.s q.s Fragrance q.s. q.s. Deionized water q.s. q.s. to 100% Viscosity(24 hrs.) 33,000 39,200

EXAMPLES 52 Hydro-Alcoholic Spray

[0201] Example 52 illustrates the use of about 1.5 (Ex. 52A) and about 2(Ex. 52B) active weight % of Polymer M of Example 1 in a spraycomposition having a low volatile organic compounds (VOC) contentemploying a hydro-alcoholic solvent system comprising 55% ethanol andwater, neutralizing amine (AMP), preservative and fragrance as shown inTable 13. TABLE 13 Ex. 52A Ex. 52B Ingredients Weight % Weight % PolymerM 1.5 2 Ethanol, SD 40 55 55 AMP (95%) To pH 6.9 To pH 6.7 Preservativeq.s. q.s. Deionized water to 100% q.s. q.s. Fragrance q.s. q.s.

[0202] The formulations showed a good, substantially uniform spraypattern when dispensed from a manually actuated pump spray and weresuitable for use in low VOC sprays, such as those desired for hair careapplications.

EXAMPLE 53 Facial Scrub

[0203] Example 53 illustrates the clarity, thickening and suspensionefficacy of inventive Polymer A of Example 1 (Ex. 53A) and anon-crosslinked Comparative HASE Polymer, CP-2 (Ex. 53B), in thefollowing high surfactant, low pH formulation shown in Table 14 at anactive polymer weight of about 1.5% suitable as a facial scrub. TABLE 14Ingredients (INCI/Trade Name) Wt. %  1. Polymer as indicated below inTable 15 1.5  2. Sodium C₁₄-C₁₆ Olefin sulfonate (40%) (Note 2) 45  3.NaOH (18%) To pH 6.5 q.s.  4. Glycerin 2  5. Salicylic acid (USP) 2  6.Jojoba esters (Note 3) 2  7. Cocamidopropyl betaine (35%) 10  8.Fragrance q.s.  9. FD&C Red 33 (0.1%) 0.1 10. D&C Yellow # 6 (0.1%) 0.211. Citric acid (50%) To pH 5.2-5.4 q.s. 12. Deionized water To 100%q.s.

[0204] The composition was prepared by pre-gelling ingredient #1 bydispersing it in a portion of the water (#12), admixing therein aportion of the primary surfactant, ingredient #2, with mild stirring toavoid aeration, and neutralizing the polymer admixture with ingredient#3 to about pH 6.5 and then adjusting the pH of the resulting gel toabout pH 5.2-5.4 with ingredient #11 to provide a gel phase. Separately,ingredients #4, 5 and the remaining portions of the water (#12) andprimary surfactant (#2) were admixed to dissolve and the resultingsolution was added slowly with mild mixing agitation to the gel phase.The secondary surfactant, ingredient #7, and remaining ingredients (#6,8, 9 and 10) were then added, taking care to avoid aerating agitation.The turbidity was determined before adding the product colorants. Thefinal pH and viscosity was measured after 24 hours aging at ambient roomtemperature (about 25° C.). The results are shown in Table 15. TABLE 15Ex. 53B Ex. 53A (Comparative (Polymer A) Polymer CP-2) Final pH 4 4Viscosity (#6 @ 20 rpm), mPa · s 14,600 11,500 Turbidity NTU (Beforecolor) 41.5 128

[0205] The composition containing Polymer A (Ex. 53A) had good claritywhereas the composition containing Comparative Polymer CP-2 (Ex. 53B)was turbid. Suspension of the jojoba beads was visually assessed after12 weeks accelerated storage aging in an oven at about 45° C. Bothpolymers maintained a stable suspension of the jojoba ester beads duringaccelerated aging.

EXAMPLE 54 Surfactant Cleansers

[0206] This example illustrates the clarity, viscosity and suspendingproperties of ASAP of Example 1, Polymer M (Ex. 54A), Polymer U (Ex.54B), Polymer AK (Ex. 54C), and Polymer D (Ex. 54D) and that ofcomparative polymer, CP-6, of Example 1 (Ex. 54E), each at an activepolymer concentration of about 2 weight % employing the formulationprovided in Table 16, suitable for use as a body wash, skin cleanser orshampoo. TABLE 16 Ingredients (INCI/Trade Name) Wt %  1. Polymer, asindicated below in Table 17 2  2. Sodium laureth sulfate (28%) (Note 4)30  3. NaOH (18%) to pH indicated q.s.  4. Propylene glycol 2  5.Cocamidopropyl betaine (35%) 4  6. EDTA, Disodium 0.1  7. Preservativeq.s.  8. U.V. Absorber q.s.  9. Fragrance solubilized in Polysorbate-20q.s. 10. FD&C Blue #1 (0.1%) 0.05 11. D&C Yellow #10 (0.1%) 1.5 12.Vitamin E (and) Gelatin beads (Note 5) 1 13. Deionized water To 100%q.s.

[0207] The compositions were prepared by pre-gelling ingredient #1 bydispersing it in a portion of the water (#13), admixing the primarysurfactant, ingredient #2, therein with gentle stirring agitation toavoid foaming, neutralizing the polymer mixture to about pH 6.7 withingredient #3, and adding ingredient #4 to the neutralized polymermixture to provide a gel phase. Separately, ingredients #6 and 8 werepremixed with the remaining portion of the water (#13), heating todissolve and then adding the resultant solution to the gel phase. Thesecondary surfactant, ingredient #5, was then added to the resultingmixture with gentle stirring agitation, followed by addition of theremaining ingredients, #9, 7, 12, 10 and 11 and the final pH adjustedwith ingredient #3, if necessary.

[0208] The % clarity was evaluated by Method B before adding the productcolorants. After 24 hours and after accelerated aging of the products inan oven at about 45° C. for up to about 12 weeks, the pH and viscositywere again determined. The results are shown in Table 17. TABLE 17 Ex.54A Ex. 54B Ex. 54C Ex. 54D Ex. 54E Polymer M Polymer U Polymer AKPolymer D Polymer CP-6 pH 6.7 6.6 6.6 6.6 6.5 Visc. (#4@20 rpm), 1,6601,800 7,300 8,400 456 mPa · s % Clarity 86.4 85.7 — — 25.2 (Beforecolor) Storage Stability 12 Weeks 12 Weeks 10 Weeks 8 Weeks — @ 45° C.pH 6.51 6.5 — — — Visc. (#4@20 rpm), 2,900 3,330 10,280 7,000 — mPa · s

[0209] The suspension of the water-insoluble beads (ingredient #12) wasvisually assessed. Initially only a few beads settled during theformation of the composition or over a 24-hour period. Duringaccelerated aging storage at about 45° C., the beads remainedsubstantially suspended (slight settling) for a period of about 12 weeksin the compositions containing Polymer M (Ex. 54A) and Polymer U (Ex.54B). The suspension of the beads was also judged substantially stablefor a period of about eight weeks in the composition containing PolymerAK (Ex. 54C) and for a period of about four weeks in the compositioncontaining Polymer D (Ex. 54D).

[0210] In contrast, the beads were not suspended by the ComparativePolymer CP-6 (Ex. 54E) and settled out of the composition in less than24 hours.

EXAMPLE 55 Emulsions

[0211] This example illustrates the use of about 1% active polymerweight ASAP of Example 1, Polymer N (Ex. 55A) and Polymer M (Ex. 55B),each in oil-in-water emulsions suitable for use as hand and body lotionsor creams, as shown in Table 18. TABLE 18 Ex. 55A Ex. 55B Ingredients(INCI/Trade Name) Weight % Weight % Mineral oil 8 8 Octyl stearate 4.54.5 Lanolin 0.5 0.5 Cetyl alcohol 1.5 1.5 Glyceryl stearate 5 5Dimethicone 0.1 0.1 Polymer 1 1 Deionized water to 100% q.s. q.s. NaOH,10% To pH 6.1 To pH 6.5 Glycerin — 3 Propylene glycol 2 2 Preservative0.5 0.5 Fragrance q.s q.s Viscosity, mPa · s 20,050 14,800 Appearance atRT glossy, white glossy, white lotion lotion Feel on skin Non-tacky &Non-tacky & smooth feel smooth feel Viscosity, mPa · s after Aging for14 Weeks Room Temperature (about 25° C.) — 18,200 35° C. — 16,400 50° C.— 12,600 Appearance after accelerated storage smooth smooth

EXAMPLE 56 Liquid Surfactant

[0212] This example illustrates the use of Polymer A of Example 1 (Ex.56A), which contains two associative monomers, and Comparative HASEPolymer CP-2 of Example 1 (Ex. 56B), which contains one associativemonomer, each at an active polymer weight of about 1.5%, employed in aliquid surfactant suitable for use as a hand dishwashing liquid havingthe formulation shown in Table 19. TABLE 19 Ingredient Wt % Polymer, asindicated below in Table 20 1.5 Ammonium lauryl sulfate (30%) 25 Sodiumlaureth sulfate (30%) (Note 4, Table 16) 25 Sodium citrate 0.5 Sodiumhydroxide (18%) to pH 6.5-7 q.s. Deionized Water to 100% q.s.

[0213] The composition can be prepared by adding the surfactants to anaqueous solution of the polymer with slow mixing agitation to avoidexcessive foam generation, adding the sodium citrate to dissolve, andadjusting the pH with sodium hydroxide. If desired, fragrance andproduct colorant also can be added. The viscosity and turbidity at aboutpH 6.5-7 are shown in Table 20. TABLE 20 Ex. 56B Ex. 56A ComparativePolymer A Polymer CP-2 Viscosity mPa · s 16,600 21,000 Turbidity NTU20.3 108.3

[0214] Polymer A (Ex. 56A) produced a substantially clear compositionwhereas the Comparative HASE Polymer CP-2 (Ex. 56B) produced a turbidcomposition.

[0215] The foregoing formulations were each further acidified withcitric acid to about pH 5 to provide a lower viscosity product. Theviscosity and turbidity at about pH 5 are shown in Table 21. TABLE 21Ex. 56B-pH 5 Ex. 56A-pH 5 Comparative Polymer A Polymer CP-2 ViscositymPa · s 5,700 4,200 Turbidity NTU 34.9 90

[0216] Again, Polymer A (Ex. 56A-pH 5) produced a significantly clearerproduct than did Comparative HASE Polymer CP-2 (Ex. 56B-pH 5).

EXAMPLE 57 Hydro-Alcoholic Gels

[0217] This example illustrates the use of an active polymer weight ofabout 1.5% Polymer L in a hydro-alcoholic gel formulation containingcamphor. The formulation shown in Table 22 had a pH of about 7.3 and aviscosity of about 5,140 mPa·s. TABLE 22 Ingredient Weight % Polymer L1.5 EDTA, Disodium 0.1 Isopropyl alcohol 10 Camphor (crystals) 0.2Polysorbate 20 1 Triethanolamine (TEA, 99%) to pH 7.3 q.s. Preservative0.2 FD&C Blue No. 1 (5%) to color q.s. Deionized water to 100% q.s.

[0218] Another series of hydro-alcoholic gel embodiments were preparedcontaining Polymer G, H, I, or J of Example 1 at an active polymerweight % of about 3.5-4%, about 10-30% ethanol, and relatively low totalamounts (<0.2%) of hair conditioning agents (Panthenol, dimethiconecopolyol), preservative, solubilized fragrance and product colorant,neutralized with TEA to a pH of about 6-6.5. These hydro-alcoholiccompositions had a viscosity in the range of about 7,500 mPa·s to about90,000 mPa·s. The specular gloss produced by these compositions wasdetermined by Method D. At an angle of 20°, the gloss value units werein the range of about 40 to about 60 and at an angle of 60°, the glossvalue units were in the range of about 85 to about 90. Thesecompositions were judged suitable for personal care and household careapplications.

EXAMPLE 58 Highly Alkaline Washing Gels

[0219] This example illustrates the use of Polymer AE and of ComparativeHASE Polymer CP-3 in a highly alkaline (pH >12.5) formulation containingdisinfectant, suitable for use as automatic dishwashing liquids, surfacecleaners and the like, employing the formulation shown in Table 23. Theresults are shown in Table 24. TABLE 23 Ingredient Weight % Polymer, asindicated below in Table 24 1 Deionized Water to 100% q.s. Rheologystabilizer (Note 6) 0.1 Potassium carbonate 5 Potassium silicate (39%)15 Potassium hydroxide (45%) 5 Sodium hydroxide (50%) 5 Sodiumtripolyphosphate 20 Sodium xylene sulfonate (40%) 0.5 Sodiumhypochlorite (12.5% Available Chlorine) 8

[0220] TABLE 24 Viscosity mPa · s at about 25° C. Polymer No. Immed. 24Hr. 1 Week AE, Ex. 1 350 1,020 36,000 CP-3, Ex. 1 350 1,120 19,500

[0221] The stability of the viscosity was judged acceptable in the art.

[0222] If higher or lower viscosity is desired, the active weight % ofthe polymer can be increased or decreased accordingly.

[0223] If desired, an oxygen releasing disinfectant, such as a hydrogenperoxide compound, may be substituted in place of the chlorine bleach.

EXAMPLE 59 Highly Alkaline Washing Liquids

[0224] This example illustrates the use of Polymer AE and of ComparativeHASE Polymer CP-3 in a highly alkaline (pH >12.5) formulation containingdisinfectant, suitable for use as substantially clear, bleach-containinglaundry prespotters, bleach-containing mold and mildew cleansers, andthe like, employing the formulation shown in Table 25. The results areshown in Table 26. TABLE 25 Ingredient Weight % Polymer, as indicated inTable 26 1 Deionized Water to 100% q.s. Rheology stabilizer (Note 6,Table 23) 0.1 Sodium hydroxide (50%) 2.5 Sodium hypochlorite (12.5%Available Chlorine) 8

[0225] TABLE 26 Viscosity mPa · s at 25° C. at 45° C. Polymer No. Immed.4 weeks 4 weeks AE, Ex. 1 2,900 6,300 5,200 CP-3, Ex. 1 2,200 5,7506,100

[0226] The products were prepared by combining the polymer, water andrheology stabilizer, adjusting the pH with the sodium hydroxide togreater than about pH 12.5, and then adding the chlorine bleach.Fragrance can be added, if desired. Alternatively, an oxygen releasingbleach, such as a hydrogen peroxide compound, may be substituted inplace of the chlorine bleach.

EXAMPLE 60 Aqueous Silicone Gels

[0227] This example illustrates the use of ASAP of Example 1, Polymers Q(Ex. 60A), Y (Ex. 60B) and Z (Ex. 60C) each in aqueous siliconepolymer-containing gels employing an active polymer weight of about 1.5%in the formulation shown in Table 27. The results are shown in Table 28.TABLE 27 Ingredient Weight % Polymer, as indicated in Table 28 1.5Deionized Water to 100% q.s. Solubilized fragrance q.s. DimethiconePEG-7 phthalate (Note 1, Table 12) 0.3 UV Stabilizer q.s. Preservativeq.s. AMP to pH as indicated in Table 28 q.s.

[0228] TABLE 28 Ex. 60A Ex. 60B Ex. 60C (Polymer Q) (Polymer Y) (PolymerZ) pH 6.9 7.1 7 Immed. Visc., mPa · s 59,800 77,800 58,000 24 Hr. Visc.,mPa · s 60,200 77,900 58,200 % Clarity 62.9 76.2 75.4

EXAMPLE 61 Aqueous Conditioning Gels

[0229] This example illustrates the use of ASAP of Example 1, Polymers Q(Ex. 61A), Y (Ex. 61B) and Z (Ex. 61C), each at an active polymer weightof about 1.2% in aqueous gels containing a cationic conditioning agentemploying the formulation shown in Table 29. The results are in Table30. TABLE 29 Ingredient Weight % Polymer, as indicated in Table 30 1.2Deionized Water to 100% q.s. Panthenol 0.1 Solubilized fragrance q.s.Polyquaternium-11 (Note 7) 0.1 Preservative q.s AMP to pH indicated inTable 30 q.s.

[0230] TABLE 30 Ex. 61A Ex. 61B Ex. 61C (Polymer Q) (Polymer Y) (PolymerZ) pH 7.1 7.1 7.1 Immed. Visc., mPa · s 41,200 37,800 48,200 24 Hr.Visc., mPa · s 38,100 38,400 79,000 % Clarity 60.5 72 71.8

EXAMPLE 62 Clear Spray Gels

[0231] This example illustrates the use of ASAP of Example 1, Polymers A(Ex. 62A), C (Ex. 62B), and Y (Ex. 62C), each an active polymer weightof about 0.8% in aqueous clear spray gels employing the formulationshown in Table 31. The results are shown in Table 32. TABLE 31Ingredient Weight % Polymer, as indicated in Table 32 0.8 DeionizedWater to 100% q.s. Glycerin 2 Preservative q.s. Triethanolamine to pHindicated in Table 32 q.s. Metal ion chelating agent q.s.

[0232] TABLE 32 Ex. 62A Ex. 62B Ex. 62C (Polymer A) (Polymer C) (PolymerY) pH 6.8 7 6.5 Immed. Visc., mPa · s 7,520 7,800 2,940 24 Hr. Visc.,mPa · s 9,440 8,040 4,600 % Clarity 73 69 82

EXAMPLE 63 Textile Treatments

[0233] This example illustrates the use of Polymer AS as a thickener ina textile print paste (Ex. 63A) and in a textile coating formulation(Ex. 63B), at the active polymer weight % indicated in Table 33. TABLE33 Weight % Ingredient Ex. 63A Ex. 63B Water to 100% q.s. q.s. PolymerAS, Ex. 1 1.5   0.76 Ammonium hydroxide (28%) to pH 9.7   8.5 Acrylicemulsion binder 5  41.86 (Note 8) (Note 9) Pigment 5 — General defoamer(Note 10) —   0.25 Ammonium nitrate (25%) —   0.45 Viscosity, mPa · s(24 hours) 28,000 244,500*

EXAMPLE 64 Conditioning Shampoo

[0234] This example illustrates the use of Polymer U of Example 1 in apearlescent conditioning shampoo at an active polymer weight of about1.5% employing the formulation shown in Table 34. TABLE 34 Ingredients(INCI/Trade Name) Wt. % Part A  1. Deionized water 40.3  2. Polymer U,Ex. 1 1.5  3. Sodium laureth sulfate (28%) (Note 4, Table 16) 30  4.NaOH (18%) to pH 6.5 q.s. Part B  5. Cocoamidopropyl hydroxysultaine(50%) 10  6. Disodium laureth sulfosuccinate (40%) 10 Part C  7.Deionized water 3  8. Mica and titanium dioxide (Note 11) 0.2 Part D  9.Dimethicone (60,000 cst) (Note 12) 3 10. Preservative q.s.    Fragranceq.s. 11. Citric Acid (50%) to pH 5.3-5.7 q.s. final weight 100

[0235] Part A of the shampoo was prepared by admixing Polymer U anddeionized water, then mixing in the surfactant (#3) with gentle mixingaction and then adjusting the mixture to a pH of about 6.5 with thealkali (#4) to provide a gel phase. The ingredients of Part B were thenadmixed into the gel phase in the order listed. The ingredients of PartC were premixed and the premix was added to the foregoing batch mixture.Ingredients #9 and #10 of Part D were then added to the batch in theorder listed and the pH of the final shampoo was adjusted withingredient #11.

[0236] The final pH of the pearlescent shampoo product was about pH 5.5,the Brookfield viscosity was about 3,640 mPa·s initially and about 4,420mPa·s after 24 hours. The pearlescent shampoo can also be prepared withmica or titanium dioxide as the opacifying, cosmetic pigment, ingredient#8.

EXAMPLES 65-69 Aqueous Gels

[0237] It is known that the viscosity achieved with commonly employedanionic polymeric thickeners can be negatively affected by the presenceof some conventional anionic polymers. This example illustrates thecompatibility of the ASAP of this invention with anionic polymericthickeners, such as carbomer polymer, and hydrophobically-modifiedcarbomer polymer, in aqueous gels.

[0238] A first series of aqueous gels (Exs. 65-69) were separatelyprepared, each gel containing one of the following ASAP of Example 1:Polymer H (Exs. 65 A-I), Polymer Y (Exs. 66 A-I), Polymer Z (Exs. 67A-I), Polymer AT (Exs. 68 A-L), Polymer AU (Exs. 69 A-I) and either acarbomer polymer, or hydrophobically-modified carbomer, as identified,and in the amount indicated, in Tables 35-39, respectively. Thecommercial thickener products employed having the INCI name, Carbomer,were: a traditional carbomer polymer, CARBOPOL® 980 polymer, and ahydrophobically-modified carbomer polymer, CARBOPOL® Ultrez 21 polymer,both sold by Noveon, Inc. (Cleveland, Ohio). Other commercialhydrophobically-modified carbomer polymers employed were: CARBOPOL® ETD2020 polymer, also sold by Noveon, Inc., having the INCI name,Acrylates/C₁₀₋₃₀ Alkyl Acrylate Crosspolymer, and STABYLEN® 30, sold by3V Inc., having the INCI name, Acrylates/Vinyl Isodecanoate.

[0239] The aqueous gels were prepared by dispersing the selectedcommercial polymeric thickener in a portion of the total water content,neutralizing the dispersion with AMP (95%) to a pH in the range-of about6-6.5, then adding the required selected amount of aqueous emulsion ofASAP of Example 1, and adjusting the water content and pH, if needed, tomaintain the foregoing pH or clarity. The pH, % clarity, and viscosity(24-hour) of the gels is shown in Tables 35-39. TABLE 35 Viscosity Ex.Active % mPa · s No. Polymer in Gel Wt. % pH Clarity (24 hours) 65APolymer H, Ex. 1 0.5 6.4 90.2 47,600 CARBOPOL ® ETD 0.5 2020 65B PolymerH, Ex. 1 0.75 6.2 84.4 64,200 CARBOPOL ® ETD 0.5 2020 65C Polymer H, Ex.1 1 6.4 89.6 65,800 CARBOPOL ® ETD 0.25 2020 65D Polymer H, Ex. 1 0.56.4 92.8 42,800 CARBOPOL ® 980 0.5 65E Polymer H, Ex. 1 0.75 6.4 90.252,000 CARBOPOL ® 980 0.5 65F Polymer H, Ex. 1 1 6.5 90.9 49,200CARBOPOL ® 980 0.25 65G Polymer H, Ex. 1 0.5 6.4 93.7 72,200 CARBOPOL ®Ultrez 21 0.5 65H Polymer H, Ex. 1 0.75 6.4 92.8 88,200 CARBOPOL ®Ultrez 21 0.5 65I Polymer H, Ex. 1 1 6.4 93.2 76,600 CARBOPOL ® Ultrez21 0.25

[0240] TABLE 36 Viscosity Ex. Active % mPa · s No. Polymer in Gel Wt. %pH Clarity (24 hours) 66A Polymer Y, Ex. 1 0.5 6.4 82.6 44,600CARBOPOL ® ETD 2020 0.5 66B Polymer Y, Ex. 1 0.75 6.3 79.8 57,800CARBOPOL ® ETD 2020 0.5 66C Polymer Y, Ex. 1 1 6.4 78.3 55,800CARBOPOL ® ETD 2020 0.25 66D Polymer Y, Ex. 1 0.5 6.4 88.1 44,700CARBOPOL ® 980 0.5 66E Polymer Y, Ex. 1 0.75 6.4 84.5 55,200 CARBOPOL ®980 0.5 66F Polymer Y, Ex. 1 1 6.4 88 50,000 CARBOPOL ® 980 0.25 66GPolymer Y, Ex. 1 0.5 6.5 91.9 63,600 CARBOPOL ® Ultrez 21 0.5 66HPolymer Y, Ex. 1 0.75 6.5 92 81,800 CARBOPOL ® Ultrez 21 0.5 66I PolymerY, Ex. 1 1 6.5 91.3 59,800 CARBOPOL ® Ultrez 21 0.25

[0241] TABLE 37 Viscosity Ex. Active % mPa · s No. Polymer in Gel Wt. %pH Clarity (24 hours) 67A Polymer Z, Ex. 1 0.5 6.3 76.9 40,200CARBOPOL ® ETD 2020 0.5 67B Polymer Z, Ex. 1 0.75 6.5 81.2 57,200CARBOPOL ® ETD 2020 0.5 67C Polymer Z, Ex. 1 1 6.4 80.9 36,200CARBOPOL ® ETD 2020 0.25 67D Polymer Z, Ex. 1 0.5 6.5 88.9 34,400CARBOPOL ® 980 0.5 67E Polymer Z, Ex. 1 0.75 6.4 81.8 42,000 CARBOPOL ®980 0.5 67F Polymer Z, Ex. 1 1 6.4 82.7 40,200 CARBOPOL ® 980 0.25 67GPolymer Z, Ex. 1 0.5 6.5 90.5 51,200 CARBOPOL ® Ultrez 21 0.5 67HPolymer Z, Ex. 1 0.75 6.5 90.1 59,800 CARBOPOL ® Ultrez 21 0.5 67IPolymer Z, Ex. 1 1 6.5 89.3 45,900 CARBOPOL ® Ultrez 21 0.25

[0242] TABLE 38 Viscosity Ex. Active % mPa · s No. Polymer in Gel Wt. %pH Clarity (24 hours) 68A Polymer AT, Ex. 1 0.5 6.5 87.5 56,400CARBOPOL ® ETD 2020 0.5 68B Polymer AT, Ex. 1 0.75 6.5 85.5 83,200CARBOPOL ® ETD 2020 0.5 68C Polymer AT, Ex. 1 1 6.5 80.9 45,600CARBOPOL ® ETD 2020 0.25 68D Polymer AT, Ex. 1 0.5 6.5 84.7 45,800CARBOPOL ® 980 0.5 68E Polymer AT, Ex. 1 0.75 6.5 82.7 62,800 CARBOPOL ®980 0.5 68F Polymer AT, Ex. 1 1 6.5 81.1 39,200 CARBOPOL ® 980 0.25 68GPolymer AT, Ex. 1 0.5 6.5 88.1 72,800 CARBOPOL ® Ultrez 21 0.5 68HPolymer AT, Ex. 1 0.75 6.5 84.6 98,200 CARBOPOL ® Ultrez 21 0.5 68IPolymer AT, Ex. 1 1 6.5 84.5 67,400 CARBOPOL ® Ultrez 21 0.25 68JPolymer AT, Ex. 1 0.5 6.5 77.8 39,400 STABYLEN ® 30 0.5 68K Polymer AT,Ex. 1 0.75 6.4 71.8 43,200 STABYLEN ® 30 0.5 68L Polymer AT, Ex. 1 1 6.466.5 31,800 STABYLEN ® 30 0.25

[0243] TABLE 39 Viscosity Ex. Active % mPa · s No. Polymer in Gel Wt. %pH Clarity (24 hours) 69A Polymer AU, Ex. 1 0.5 6.4 88.6 57,800CARBOPOL ® ETD 2020 0.5 69B Polymer AU, Ex. 1 0.75 6.5 89.5 73,400CARBOPOL ® ETD 2020 0.5 69C Polymer AU, Ex. 1 1 6.5 87.9 55,800CARBOPOL ® ETD 2020 0.25 69D Polymer AU, Ex. 1 0.5 6.5 89.9 43,400CARBOPOL ® 980 0.5 69E Polymer AU, Ex. 1 0.75 6.5 89.8 58,200 CARBOPOL ®980 0.5 69F Polymer AU, Ex. 1 1 6.5 89.3 47,600 CARBOPOL ® 980 0.25 69GPolymer AU, Ex. 1 0.5 6.5 89.2 70,000 CARBOPOL ® Ultrez 21 0.5 69HPolymer AU, Ex. 1 0.75 6.5 85.8 79,800 CARBOPOL ® Ultrez 21 0.5 69IPolymer AU, Ex. 1 1 6.5 88.5 51,600 CARBOPOL ® Ultrez 21 0.25

[0244] A second series of aqueous gels containing each of the foregoingASAP was prepared following the procedure described above except that,after the selected commercial thickener was dispersed in water, theselected ASAP was added and the resulting combination was thenneutralized with AMP (95%) to about pH 6-6.5. The % clarity and 24-hourviscosity results achieved for this second series of aqueous gels weresubstantially similar to those of the corresponding ASAP-containing gelsin the first series of aqueous gels.

[0245] The results show that the ASAP of this invention can be employedin combination with either conventional carbomer, or modified carbomer,thickeners in aqueous gel, without sacrificing viscosity.

[0246] For comparison, the viscosity achieved in an aqueous gel with theAMP-neutralized commercial polymer in the absence of ASAP is shown inTable 40. TABLE 40 Active Viscosity mPa · s Polymer in Gel Wt. % pH (24hours) CARBOPOL ® ETD 2020 0.5 6.3 26,500-26,600 CARBOPOL ® ETD 20200.25 6.3 16,650 CARBOPOL ® 980 0.5 6.4 43,800 CARBOPOL ® 980 0.25 6.427,900 CARBOPOL ® Ultrez 21 0.5 6.4 46,800-46,950 CARBOPOL ® Ultrez 210.25 6.4 35,600 STABYLEN ® 30 0.5 6.5 16,100 STABYLEN ® 30 0.25 6.512,600

EXAMPLE 70 Aqueous Gels

[0247] This example demonstrates the use of ASAP, Polymer AT of Example1, in combination with commercial hydrophobically-modified carbomerpolymer, CARBOPOL® Ultrez 21 (Noveon, Inc., Cleveland Ohio) inbeneficially achieving an unexpected increase in viscosity whilemaintaining the desirable aesthetic and gel pick-up product propertiesassociated with gels produced with such commercially available polymer.

[0248] Aqueous gels were prepared containing the varying amounts of eachpolymer shown in Table 41 below. The gels were prepared by adding thecommercial polymer to the water and pre-dispersing it by admixing withstirring for about 15 minutes, avoiding entraining air, and allowing theadmixture to stand without stirring for about 30 minutes to provide apolymer dispersion. The requisite amount of Polymer AT emulsion was thenadmixed into the foregoing polymer dispersion and sufficient AMP (95%)was added to the polymeric mixture to adjust the pH to a range of about6.4-6.8 to form a gel.

[0249] Two series of gels were prepared containing, on a compositionweight basis, either a total polymer content of about 1.25 active weight% (Ex. 70A-F) or about 1 active weight % (Ex. 70G-K). The viscosity wasdetermined by Method A. Gel pick-up was subjectively evaluated bydipping three fingers into the gel to scoop a dollop of gel andobserving the cushioning properties of the gel adhering to the fingers.The term “cushioning” refers generally to the firmness of a gel and theability of a dollop of gel to adhere to the fingers and hold a firm peak(i.e., a peaking gel). Gel pick-up was subjectively rated on the basisof observed cushioning as follows: excellent=pronounced and sustainedpeak, very good=medium and sustained peak, good=slight to medium peak,marginal=slight peak, and weak=no peak, smooth. Gel pick-up is a sensoryproduct attribute that a consumer observes when the user physicallyremoves gel from a container, such as a jar, or squeezes a gel out of atube onto the fingers for application to the skin or hair. The resultsof the viscosity and gel pick-up evaluations are shown in Table 41.TABLE 41 Weight % Weight % Brookfield Example Polymer AT, CARBOPOL ®Viscosity No. (Ex. 1) Ultrez 21 (mpa · s) Gel Pick-Up 70A 1.25 — 21,200Weak 70B 1 0.25 60,400 Good 70C 0.75 0.5 97,600 Very Good 70D 0.5 0.75125,000 Excellent 70E 0.25 1 125,000 Excellent 70F — 1.25 93,600Excellent 70G 1 — 11,400 Marginal 70H 0.75 0.25 21,800 Good 70I 0.5 0.567,200 Very Good 70J 0.25 0.75 93,800 Excellent 70K — 1 76,600 Excellent

[0250] The results show an unexpected increase in viscosity was achievedat a total polymer content of about 1.25 active weight % when the weightratio of ASAP: commercial polymer was about 3:2 (Ex. 70C), about 2:3(Ex. 70D) and about 1:4 (Ex. 70E). At a total polymer content of about 1active weight %, an unexpected increase in viscosity was achieved whenthe weight ratio of ASAP: commercial polymer was about 1:3 (Ex. 70J).

[0251] The gel pick-up of Exs. 70B-E and Exs. 70H-J was judged good toexcellent, indicating the compatibility of ASAP with the commercialpolymer.

[0252] It was surprisingly found that alkali-swellable ASAP can be usedin combination with anionic polymeric thickener, such as carbomerpolymer or hydrophobically modified carbomer polymer, to provide aviscosity that is unexpectedly higher than the sum of the viscosity ofthe individual polymers at the same concentration.

[0253] From the foregoing examples, it can be seen that the presentinventive polymers can be used in a wide variety of different aqueousand hydro-alcoholic compositions. The foregoing discussion and reportedstudies are intended to be illustrative of the present invention and arenot to be taken as limiting. Still other variants within the spirit andscope of this invention are possible and will readily present themselvesto those skilled in the art.

We claim:
 1. An associative polymer that is the product ofpolymerization of a monomer mixture comprising: (a) at least one acidicvinyl monomer or a salt thereof; (b) at least one nonionic vinylmonomer; (c) a first associative monomer, having a first hydrophobic endgroup; (d) at least one monomer selected from the group consisting of asecond associative monomer, having a second hydrophobic end group, asemihydrophobic monomer, and a combination thereof; and, optionally, (e)a monomer selected from the group consisting of a crosslinking monomer,a chain transfer agent, and a combination thereof; with the proviso thatwhen monomer (d) is a second associative monomer, the first and secondhydrophobic end groups of associative monomers (c) and (d) are eachindependently selected from the same or different hydrocarbon classes,and when the first and second hydrophobic end groups are selected fromthe same hydrocarbon class, the molecular formulas of the hydrophobicend groups differ by at least about 8 carbon atoms.
 2. The polymer ofclaim 1 wherein the acidic vinyl monomer is selected from the groupconsisting of a carboxylic acid-containing vinyl monomer, a sulfonicacid-containing vinyl monomer, a phosphonic acid-containing vinylmonomer, and a combination thereof.
 3. The polymer of claim 1 whereinthe acidic vinyl monomer is acrylic acid, methacrylic acid,styrenesulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, or acombination thereof.
 4. The polymer of claim 1 wherein the salt isselected from the group consisting of an alkali metal salt, an alkalineearth metal salt, an ammonium salt, an alkyl-substituted ammonium salt,and a combination thereof.
 5. The polymer of claim 1 wherein thenonionic vinyl monomer is a compound having one of the followingformulas (I) or (II): CH₂═C(X)Z  (I) CH₂═CH—OC(O)R  (II) wherein, ineach of formulas (I) and (II), X is H or methyl; Z is —C(O)OR¹,—C(O)NH₂, —C(O)NHR¹, —C(O)N(R¹)₂, —C₆H₄R¹, —C₆H₄OR¹, —C₆H₄Cl, —CN,—NHC(O)CH₃, —NHC(O)H, N-(2-pyrrolidonyl), N-caprolactamyl,—C(O)NHC(CH₃)₃, —C(O)NHCH₂CH₂—N-ethyleneurea, —SiR₃,—C(O)O(CH₂)_(x)SiR₃, —C(O)NH(CH₂)_(x)SiR₃, or —(CH₂)_(x)SiR₃; x is aninteger in the range of 1 to about 6; each R is independently C₁-C₁₈alkyl; each R¹ is independently C₁-C₃₀ alkyl, hydroxy-substituted C₁-C₃₀alkyl, or halogen-substituted C₁-C₃₀ alkyl.
 6. The polymer of claim 1wherein the nonionic vinyl monomer is selected from the group consistingof a C₁-C₈ ester of acrylic acid, a C₁-C₈ ester of methacrylic acid, anda combination thereof.
 7. The polymer of claim 1 wherein the first andsecond associative monomers each comprise a polymerizable, unsaturatedend group, a C₈-C₄₀ alkyl hydrophobic end group, and a polyoxyalkylenegroup disposed between and covalently bonded to the unsaturated endgroup and the hydrophobic end group.
 8. The polymer of claim 7 whereinthe polyoxyalkylene group is a homopolymer, a random copolymer, or ablock copolymer comprising about 5 to about 250 C₂-C₄ oxyalkylene units.9. The polymer of claim 1 wherein the first associative monomer and thesecond associative monomer are each independently compounds having thefollowing formula (III):

wherein, each R² is independently H, methyl, —C(O)OH, or —C(O)OR³; R³ isC₁-C₃₀ alkyl; A is —CH₂C(O)O—, —C(O)O—, —O—, —CH₂O—, —NHC(O)NH—,—C(O)NH—, —Ar-(CE₂)_(z)—NHC(O)O—, —Ar-(CE₂)_(z)—NHC(O)NH—, or—CH₂CH₂NHC(O)—; Ar is a divalent aryl; E is H or methyl; z is 0 or 1; kis an integer in the range of 0 to about 30, and m is 0 or 1, with theproviso that when k is 0, m is 0, and when k is in the range of 1 toabout 30, m is 1; (R⁴—O)_(n) is a polyoxyalkylene, which is ahomopolymer, a random copolymer, or a block copolymer of C₂-C₄oxyalkylene units, wherein R⁴ is C₂H₄, C₃H₆, C₄H₈, and n is an integerin the range of about 5 to about 250, Y is —R⁴O—, —R⁴NH—, —C(O)—,—C(O)NH—, —R⁴NHC(O)NH—, or —C(O)NHC(O)—; and R⁵ is a substituted orunsubstituted alkyl selected from the group consisting of a C₈-C₄₀linear alkyl, a C₈-C₄₀ branched alkyl, a C₈-C₄₀ carbocyclic alkyl, aC₂-C₄₀ alkyl-substituted phenyl, an aryl-substituted C₂-C₄₀ alkyl, and aC₈-C₈ ₀ complex ester; wherein the R⁵ alkyl group optionally comprisesone or more substituents selected from the group consisting of ahydroxyl group, an alkoxyl group, and a halogen group.
 10. The polymerof claim 1 wherein monomer (d) is a second associative monomer; thefirst associative monomer (c) and the second associative monomer (d)each having a hydrophobic end group independently selected from thegroup of hydrocarbon classes consisting of a C₈-C₄₀ linear alkyl, aC₈-C₄₀ branched alkyl, a C₈-C₄₀ carbocyclic alkyl, a C₂-C₄₀alkyl-substituted phenyl, an aryl-substituted C₂-C₄₀ alkyl, and a C₈-C₁₀complex ester.
 11. The polymer of claim 1 wherein the monomer mixtureincludes at least one semihydrophobic monomer having a polymerizable,unsaturated end group and a polyoxyalkylene group covalently bondedthereto.
 12. The polymer of claim 11 wherein the polyoxyalkylene groupis a homopolymer, a random copolymer, or a block copolymer comprisingabout 5 to about 250 C₂-C₄ oxyalkylene units.
 13. The polymer of claim 1wherein the monomer mixture includes at least one semihydrophobicmonomer (d) which is a compound having one of the following formulas(IV) or (V):

wherein, in each of formulas (IV) and (V), each R⁶ is independently H,C₁-C₃₀ alkyl, —C(O)OH, or —C(O)OR⁷; R⁷ is C₁-C₃₀ alkyl; A is —CH₂C(O)O—,—C(O)O—, —O—, —CH₂O—, —NHC(O)NH—, —C(O)NH—, —Ar-(CE₂)_(z)—NHC(O)O—,—Ar-(CE₂)_(z)—NHC(O)NH—, or —CH₂CH₂NHC(O)—; Ar is a divalent aryl; E isH or methyl; z is 0 or 1; p is an integer in the range of 0 to about 30,and r is 0 or 1, with the proviso that when p is 0, r is 0, and when pis in the range of 1 to about 30, r is 1; (R⁸—O)_(v) is apolyoxyalkylene, which is a homopolymer, a random copolymer or a blockcopolymer of C₂-C₄ oxyalkylene units, wherein R⁸ is C₂H₄, C₃H₆, C₄H₈,and v is an integer in the range of about 5 to about 250, R⁹ is H orC₁-C₄ alkyl; and D is a C₈-C₃₀ unsaturated alkyl or acarboxy-substituted C₈-C₃₀ unsaturated alkyl.
 14. The polymer of claim 1wherein the monomer mixture includes a semihydrophobic monomer havingone of the following chemical formulas:CH₂═CH—O—(CH₂)_(a)—O—(C₃H₆₀)_(b)—(C₂H₄O)_(c)—H orCH₂═CH—CH₂—O—(C₃H₆O)_(d)—(C₂H₄O)_(e)—H; wherein a is 2, 3, or 4; b is aninteger in the range of 1 to about 10; c is an integer in the range ofabout 5 to about 50; d is an integer in the range of 1 to about 10; ande is an integer in the range of about 5 to about
 50. 15. The polymer ofclaim 1 wherein the monomer mixture contains at least one cross linkingmonomer.
 16. The polymer of claim 15 wherein the crosslinking monomer isan acrylate ester of a polyol having at least two acrylate ester groups,a methacrylate ester of a polyol having at least two methacrylate estergroups or a combination thereof.
 17. The polymer of claim 1 wherein themonomer mixture contains at least one chain transfer agent.
 18. Thepolymer of claim 17 wherein the chain transfer agent is selected fromthe group consisting of a thio compound, a disulfide compound, aphosphite, a hypophosphite, a haloalkyl compound, and a combinationthereof.
 19. A process for the preparation of an associative polymer ofclaim 1 comprising emulsion polymerizing the monomer mixture in anaqueous medium, at a pH of not more than about 4, in the presence of afree radical initiator, and at a reaction temperature in the range ofabout 30 to about 95° C.
 20. The process of claim 19 wherein theemulsion polymerization is carried out in the presence of an emulsifyingamount of an anionic surfactant, a nonionic surfactant, an amphotericsurfactant, or a combination thereof.
 21. An associative polymerproduced by the emulsion polymerization process of claim
 19. 22. Acomposition comprising an associative polymer of claim 1 and waterhaving a pH of greater than about
 2. 23. The composition of claim 22further comprising a pH adjusting agent, a buffering agent, a fixative,a film former, an auxiliary rheology modifier, a hair conditioningagent, a skin conditioning agent, a chemical hair waving orstraightening agent, a colorant, a surfactant, a polymer film modifyingagent, a product finishing agent, a propellant, or a mixture thereof.24. The composition of claim 22 further comprising a carbomer polymer ora hydrophobically-modified carbomer polymer.
 25. The composition ofclaim 22 further comprising a silicone polymer.
 26. The composition ofclaim 22 further comprising a C₁-C₈ monohydric alcohol, a C₁-C₈ polyolor mixture thereof.
 27. The composition of claim 22 in the form of aliquid, a gel, a spray, an emulsion, a semisolid, or a solid.
 28. Aformulated composition comprising an associative polymer of claim 1wherein the formulated composition is selected from a composition forpersonal care, health care, household care, institutional and industrialcare, and industrial processes.
 29. The formulated composition of claim28 wherein the composition for personal care is a cleanser for skin orhair.
 30. The formulated composition of claim 28 wherein the compositionfor personal care or health care includes a pH adjusting agent, abuffering agent, a fixative, a film former, an auxiliary rheologymodifier, a hair conditioning agent, a skin conditioning agent, achemical hair waving or straightening agent, a colorant, a surfactant, apolymer film modifying agent, a product finishing agent, a propellant,or a mixture thereof.
 31. The formulated composition of claim 28 whereinthe composition for household care or institutional and industrial careis a cleanser.
 32. The formulated composition of claim 28 wherein thecomposition for household care or institutional and industrial careincludes a pH adjusting agent, a buffering agent, a film former, anauxiliary rheology modifier, a colorant, a surfactant, a metal ionchelating agent, a dispersant, a propellant, or a mixture thereof. 33.The formulated composition of claim 28, wherein the composition forindustrial processes is a textile treatment.
 34. The formulatedcomposition of claim 28, wherein the composition for household care,institutional and industrial care, or industrial processes is a paint orsurface coating.
 35. The composition of claim 28 in the form of aliquid, a gel, a spray, an emulsion, a semisolid, or a solid.
 36. Anassociative polymer that is the product of polymerization of a monomermixture comprising, on a total monomer mixture weight basis: (a) about10 to about 75 weight percent of at least one acidic vinyl monomer or asalt thereof; (b) about 10 to about 90 weight percent of at least onenonionic vinyl monomer; (c) about 0.1 to about 25 weight percent of afirst associative monomer having a first hydrophobic end group; (d)about 0.1 to about 25 weight percent of at least one monomer selectedfrom the group consisting of a second associative monomer having asecond hydrophobic end group, a semihydrophobic monomer, and acombination thereof; and, optionally, (e) up to about 20 weight percentof a monomer selected from the group consisting of a crosslinkingmonomer, a chain transfer agent, and a combination thereof; with theproviso that when monomer (d) is a second associative monomer, the firstand second hydrophobic end groups of associative monomers (c) and (d)are each independently selected from the-same or different hydrocarbonclasses, and when the first and second hydrophobic end groups areselected from the same hydrocarbon class, the molecular formulas of thehydrophobic end groups differ by at least about 8 carbon atoms.
 37. Thepolymer of claim 36 wherein the acidic vinyl monomer is selected fromthe group consisting of a carboxylic acid-containing vinyl monomer, asulfonic acid-containing vinyl monomer, a phosphonic acid-containingvinyl monomer, and a combination thereof.
 38. The polymer of claim 36wherein the acidic vinyl monomer is acrylic acid, methacrylic acid,styrenesulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, or acombination thereof.
 39. The polymer of claim 36 wherein the salt isselected from the group consisting of an alkali metal salt, an alkalineearth metal salt, an ammonium salt, an alkyl-substituted ammonium salt,and a combination thereof.
 40. The polymer of claim 36 wherein thenonionic vinyl monomer is a compound having one of the followingformulas (I) or (II): CH₂═C(X)Z  (I) CH₂═CH—OC(O)R  (II) wherein, ineach of formulas (I) and (II), X is H or methyl; Z is —C(O)OR¹,—C(O)NH₂, —C(O)NHR¹, —C(O)N(R¹)₂, —C₆H₄R¹, —C₆H₄₀R¹, —C₆H₄Cl—CN,—NHC(O)CH₃, —NHC(O)H, N-(2-pyrrolidonyl), N-caprolactamyl,—C(O)NHC(CH₃)₃, —C(O)NHCH₂CH₂—N-ethyleneurea, —SiR₃,—C(O)O(CH₂)_(x)SiR₃, —C(O)NH(CH₂)_(x)SiR₃, or —(CH₂)_(x)SiR₃; x is aninteger in the range of 1 to about 6; each R is independently C₁-C₁₈alkyl; each R¹ is independently C₁-C₃₀ alkyl, hydroxy-substituted C₁-C₃₀alkyl, or halogen-substituted C₁-C₃₀ alkyl.
 41. The polymer of claim 36wherein the nonionic vinyl monomer is selected from the group consistingof a C₁-C₈ ester of acrylic acid, a C₁-C₈ ester of methacrylic acid, anda combination thereof.
 42. The polymer of claim 36 wherein the first andsecond associative monomers each comprise a polymerizable, unsaturatedend group, a C₈-C₄₀ alkyl hydrophobic end group, and a polyoxyalkylenegroup disposed between and covalently bonded to the unsaturated endgroup and the hydrophobic end group.
 43. The polymer of claim 42 whereinthe polyoxyalkylene group is a homopolymer, a random copolymer, or ablock copolymer comprising about 5 to about 250 C₂-C₄ oxyalkylene units.44. The polymer of claim 36 wherein the first and second associativemonomers are each independently selected from compounds having thefollowing formula (III):

wherein, each R² is independently H, methyl, —C(O)OH, or —C(O)OR³; R³ isC₁-C₃₀ alkyl; A is —CH₂C(O)O—, —C(O)O—, —O—, —CH₂O—, —NHC(O)NH—,—C(O)NH—, —Ar-(CE₂)_(z)—NHC(O)O—, —Ar-(CE₂)_(z)—NHC(O)NH—, or—CH₂CH₂NHC(O)—; Ar is a divalent aryl; E is H or methyl; z is 0 or 1; kis an integer in the range of 0 to about 30, and m is 0 or 1, with theproviso that when k is 0, m is 0, and when k is in the range of 1 toabout 30, m is 1; (R⁴—O)_(n) is a polyoxyalkylene, which is ahomopolymer, a random copolymer or a block copolymer of C₂-C₄oxyalkylene units, wherein R⁴ is C₂H₄, C₃H₆, or C₄H₈, and n is aninteger in the range of about 5 to about 250; Y is —R⁴O—, —R⁴NH—,—C(O)—, —C(O)NH—, —R⁴NHC(O)NH—, or —C(O)NHC(O)—; and R⁵ is a substitutedor unsubstituted alkyl selected from the group consisting of a C₈-C₄₀linear alkyl, a C₈-C₄₀ branched alkyl, a C₈-C₄₀ carbocyclic alkyl, aC₂-C₄₀ alkyl-substituted phenyl, an aryl-substituted C₂-C₄₀ alkyl, and aC₈-C₈₀ complex ester; wherein the R⁵ alkyl group optionally comprisesone or more substituents selected from the group consisting of ahydroxyl group, an alkoxyl group, and a halogen group.
 45. The polymerof claim 36 wherein the monomer mixture includes at least onesemihydrophobic monomer having a polymerizable, unsaturated end groupand a polyoxyalkylene group covalently bonded thereto.
 46. The polymerof claim 45 wherein the polyoxyalkylene group is a homopolymer, a randomcopolymer, or a block copolymer comprising about 5 to about 250 C₂-C₄oxyalkylene units.
 47. The polymer of claim 36 wherein monomer mixtureincludes at least one semihydrophobic monomer which is a compound havingone of the following formulas (IV) or (V):

wherein, in each of formulas (IV) and (V), each R⁶ is independently H,C₁-C₃₀ alkyl, —C(O)OH, or —C(O)OR⁷; R⁷ is C₁-C₃₀ alkyl; A is —CH₂C(O)O—,—C(O)O—, —O—, —CH₂O—, —NHC(O)NH—, —C(O)NH—, —Ar-(CE₂)_(z)—NHC(O)O—,—Ar-(CE₂)_(z)—NHC(O)NH—, or —CH₂CH₂NHC(O)—; Ar is a divalent aryl; E isH or methyl; z is 0 or 1; p is an integer in the range of 0 to about 30,and r is 0 or 1, with the proviso that when p is 0, r is 0, and when pis in the range of 1 to about 30, r is 1; (R⁸—O)_(v) is apolyoxyalkylene, which is a homopolymer, a random copolymer, or a blockcopolymer of C₂-C₄ oxyalkylene units, wherein R⁸ is C₂H₄, C₃H₆, or C₄H₈,and v is an integer in the range of about 5 to about 250, preferably R⁹is H or C₁-C₄ alkyl; and D is a C₈-C₃₀ unsaturated alkyl, or acarboxy-substituted C₈-C₃₀ unsaturated alkyl.
 48. The polymer of claim36 wherein the monomer mixture includes a semihydrophobic monomer havingone of the following chemical formulas:CH₂═CH—O—(CH₂)_(a)—O—(C₃H₆O)_(b)—(C₂H₄O)_(c)—H orCH₂═CH—CH₂—O—(C₃H₆O)_(d)—(C₂H₄O)_(e)—H; wherein a is 2, 3, or 4; b is aninteger in the range of 1 to about 10; c is an integer in the range ofabout 5 to about 50; d is an integer in the range of 1 to about 10; ande is an integer in the range of about 5 to about
 50. 49. The polymer ofclaim 36 wherein the monomer mixture includes about 0.1 to about 2weight percent of a crosslinking monomer.
 50. The polymer of claim 49wherein the crosslinking monomer is an acrylate ester of a polyol havingat least two acrylate ester groups, a methacrylate ester of a polyolhaving at least two methacrylate ester groups or a combination thereof.51. The polymer of claim 36 wherein the monomer mixture includes about0.1 to about 10 weight percent of at least one chain transfer agent. 52.The polymer of claim 51 wherein the chain transfer agent is selectedfrom the group consisting of a thio compound, a disulfide compound, aphosphite, a hypophosphite, a haloalkyl compound, and a combinationthereof.
 53. The polymer of claim 36 wherein monomer (d) comprises asecond associative monomer and both of the first and second hydrophobicend groups of monomers (c) and (d) comprise a C₈-C₄₀ linear alkyl group,and the molecular formulas of the first and second hydrophobic endgroups differ from one another by at least about 8 carbon atoms.
 54. Thepolymer of claim 53 wherein the molecular formulas of the first andsecond hydrophobic end groups differ from one another by at least about10 carbon atoms.
 55. An alkali-swellable associative-polymer that is theproduct of polymerization of a monomer mixture comprising, on a totalmonomer mixture weight basis: (a) about 30 to about 75 weight percent ofat least one acidic vinyl monomer or a salt thereof; (b) at least about25 weight percent, but not more than 60 weight percent of at least onenonionic vinyl monomer; (c) about 0.5 to about 20 weight percent of afirst associative monomer having a first hydrophobic end group; (d)about 0.5 to about 20 weight percent of at least one monomer selectedfrom the group consisting of a second associative monomer having asecond hydrophobic end group, a semihydrophobic monomer, and acombination thereof; and, optionally; (e) up to about 20 weight percentof a crosslinking monomer; with the proviso that when monomer (d) is asecond associative monomer, the first and second hydrophobic end groupsof associative monomers (c) and (d) are each independently selected fromthe same or different hydrocarbon classes, and when the first and secondhydrophobic end groups are selected from the same hydrocarbon class, themolecular formulas of the hydrophobic end groups differ by at leastabout 8 carbon atoms.
 56. The polymer of claim 55 wherein the acidicvinyl monomer is selected from the group consisting of a carboxylicacid-containing vinyl monomer, a sulfonic acid-containing vinyl monomer,a phosphonic acid-containing vinyl monomer, and a combination thereof.57. The polymer of claim 55 wherein the acidic vinyl monomer is acrylicacid, methacrylic acid, styrenesulfonic acid,2-acrylamido-2-methylpropane sulfonic acid, or a combination thereof.58. The polymer of claim 55 wherein the salt is selected from the groupconsisting of an alkali metal salt, an alkaline earth metal salt, anammonium salt, an alkyl-substituted ammonium salt, and a combinationthereof.
 59. The polymer of claim 55 wherein the nonionic vinyl monomeris selected from the group consisting of a C₁-C₈ ester of acrylic acid,a C₁-C₈ ester of methacrylic acid, and a combination thereof.
 60. Thepolymer of claim 55 wherein the nonionic vinyl monomer is selected fromthe group consisting of ethyl acrylate, methyl methacrylate, and acombination thereof.
 61. The polymer of claim 55 wherein the first andsecond associative monomers each comprise a polymerizable, unsaturatedend group, a C₈-C₄₀ alkyl hydrophobic end group, and a polyoxyalkylenegroup disposed between and covalently bonded to the unsaturated endgroup and the hydrophobic end group.
 62. The polymer of claim 61 whereinthe polyoxyalkylene group is a homopolymer, a random copolymer, or ablock copolymer comprising about 5 to about 250 C₂-C₄ oxyalkylene units.63. The polymer of claim 55 wherein the monomer mixture includes atleast one semihydrophobic monomer having a polymerizable, unsaturatedend group and a polyoxyalkylene group covalently bonded thereto.
 64. Thepolymer of claim 63 wherein the polyoxyalkylene group is a homopolymer,a random copolymer, or a block copolymer comprising about 5 to about 250C₂-C₄ oxyalkylene units.
 65. The polymer of claim 55 wherein the monomermixture includes a semihydrophobic monomer having one of the followingchemical formulas: CH₂═CH—O—(CH₂)_(a)—O—(C₃H₆O)_(b)—(C₂H₄O)_(c)—H orCH₂═CH—CH₂—O—(C₃H₆O)_(d)—(C₂H₄O)_(e)—H; wherein a is 2, 3, or 4; b is aninteger in the range of 1 to about 10; c is an integer in the range ofabout 5 to about 50; d is an integer in the range of 1 to about 10; ande is an integer in the range of about 5 to about
 50. 66. The polymer ofclaim 55 wherein the monomer mixture includes about 0.1 to about 2% of acrosslinking monomer.
 67. The polymer of claim 66 wherein thecrosslinking monomer is an acrylate ester of a polyol having at leasttwo acrylate ester groups, a methacrylate ester of a polyol having atleast two methacrylate ester groups or a combination thereof.
 68. Apolymer of claim 55 wherein the monomer mixture includes about 0.1 toabout 2% of a chain transfer agent.
 69. A polymer of claim 68 whereinthe chain transfer agent is selected from the group consisting of a thiocompound, a disulfide compound, a phosphite, a hypophosphite, ahaloalkyl compound, and a combination thereof.
 70. An alkali-solubleassociative polymer that is the product of polymerization of a monomermixture comprising, on a total monomer mixture weight basis: (a) about10 to about 30 weight percent of at least one acidic vinyl monomer or asalt thereof; (b) more than 60 weight percent of at least one nonionicvinyl monomer; (c) about 0.5 to about 5 weight percent of at least oneassociative monomer having a hydrophobic end group; (d) about 0.5 toabout 5 weight percent of at least one semihydrophobic monomer having apolymerizable, unsaturated end group and a polyoxyalkylene groupcovalently bonded thereto; and (e) about 0.5 to about 5 weight percentof a chain transfer agent.
 71. The polymer of claim 70 wherein theacidic vinyl monomer is selected from the group consisting of acarboxylic acid-containing vinyl monomer, a sulfonic acid-containingvinyl monomer, a phosphonic acid-containing vinyl monomer, and acombination thereof.
 72. The polymer of claim 70 wherein the acidicvinyl monomer is acrylic acid, methacrylic acid, styrenesulfonic acid,2-acrylamido-2-methylpropane sulfonic acid, or a combination thereof.73. The polymer of claim 70 wherein the salt is selected from the groupconsisting of an alkali metal salt, an alkaline earth metal salt, anammonium salt, an alkyl-substituted ammonium salt, and a combinationthereof.
 74. The polymer of claim 70 wherein the nonionic vinyl monomeris selected from the group consisting of a C₁-C₈ ester of acrylic acid,a C₁-C₈ ester of methacrylic acid, and a combination thereof.
 75. Thepolymer of claim 70 wherein the nonionic vinyl monomer is selected fromthe group consisting of ethyl acrylate, methyl methacrylate, and acombination thereof.
 76. The polymer of claim 75 wherein the nonionicvinyl monomer comprises a combination of ethyl acrylate and methylmethacrylate in a weight ratio of at least about 2:1, respectively. 77.The polymer of claim 70 wherein the associative monomer comprises apolymerizable, unsaturated end group, a C₈-C₄₀ alkyl hydrophobic endgroup, and a polyoxyalkylene group disposed between and covalentlybonded to the unsaturated end group and the hydrophobic end group. 78.The polymer of claim 77 wherein the polyoxyalkylene group of theassociative monomer is a homopolymer, a random copolymer, or a blockcopolymer comprising about 5 to about 250 C₂-C₄ oxyalkylene units. 79.The polymer of claim 70 wherein the polyoxyalkylene group of thesemihydrophobic monomer is a homopolymer, a random copolymer, or a blockcopolymer comprising about 5 to about 250 C₂-C₄ oxyalkylene units. 80.The polymer of claim 70 wherein the semihydrophobic monomer is acompound having one of the following chemical formulas:CH₂═CH—O—(CH₂)_(a)—O—(C₃H₆O)_(b)—(C₂H₄O)_(c)—H orCH₂═CH—CH₂—O—(C₃H₆O)_(d)—(C₂H₄O)_(c)—H; wherein a is 2, 3, or 4; b is aninteger in the range of 1 to about 10; c is an integer in the range ofabout 5 to about 50; d is an integer in the range of 1 to about 10; ande is an integer in the range of about 5 to about
 50. 81. The polymer ofclaim 70 wherein the chain transfer agent is selected from the groupconsisting of a thio compound, a disulfide compound, a phosphite, ahypophosphite, a haloalkyl compound, and a combination thereof.